Platinum Metals Review: Vol. JULY 1996 3

PLATINUM METALS REVIEW
A quarterly survey of research on the platinum metals and of

developments in their application in industry
VOL. 40
JULY 1996
NO. 3
Contents
Chiral Complexes of Platinum Metals
102
Palladium Facilitates Optical Switching
109
Emission Control Technology
110
Electronic and Nuclear Magnetism in Platinum-Iron at Ultralow Temperatures
112
Palladium Colloid Catalyst Used in Microcontact Printing
116
Platinum and Biological Systems
117
Hydrocarbonylation in Platinum Metals Metallurgy
118
Single Platinum-Rhodium Gauze for Partial Oxidation
125
Palladium Catalysts in Organic Synthesis
126
Platinum Complexes Used in DNA Binding Studies
127
Platinum 1996
127
Ruthenium: A Dance to the Music of Time
128
Abstracts
135
New Patents
143
Communications should be addressed to

The Editor, Susan V. Ashton, Platinum Metals Review
Johnson Matthey Public Limited Company, Hatton Garden, London ECl N 8 E E
Chiral Complexes of Platinum Metals

A NEW CLASS OF COMPOUNDS WITH LIGANDS DERIVED FROM
NATURALLY OCCURRING TERPENES HAVING PROMISING PROPERTIES
By Professor A. von Zelewsky

Institute of Inorganic Chemistry, University of Fribourg, Switzerland
Molecular isomerism has been known about for well over 100 years and forms
a very important part of organic chemistry It was one of the phenomena from
which the Alsatian chemist, Aljred Werner,working, often with platinum group
metals, at the University of Zurich, Switzerland (Nobel Prize for Chemistry
1918) derived his theoryof co-ordinationin 1893 ( 1 ) . However, more recently
there has been a vast increase in the amount of work done on isomerism of
co-ordination compounds, especially concerning chiral structures ( 2 ) . Thepresent paper describes some new developments on platinum metals complexes
with chiral ligands derived from terpenes, where for thefirst time the chirality
at metal centres can be controlled in a large number of compounds.
Any discussion on such specialised topics as

isomerism and chirality needs to be prefaced by
a description of some of the terms used. Coordination compounds have a central atom surrounded by other atoms or molecular entities
called ligands, which are bound or co-ordinated
to it. Some compounds are isomeric, which
means that they exist as two or more structures
with the same molecular composition but with
a different spatial composition or constitution.
Background of Isomerism
Isomerism can occur in severalways: the simplest being constitutional isomerism, where the
same atoms are connected in different ways. If,
on the other hand two molecules contain identical atoms connected together in the same
way, but with different spatial arrangement,
one speaks of stereoisomers. Molecular stereoisomers can be divided unambiguously into
two different classes: diastereoisomers and
enantiomers.
Diastereoisomers are molecules that show the
same connectivity, but differ in the spatial
arrangement of the atoms. Internal co-ordinates
(bond lengths and bond angles) will be in general different in different diastereoisomers, rendering them different chemical species in every
Platinum Metals Rev., 1996, 40, (3), 102-109
respect. A well-known example of diastereoisomers in platinum chemistry is cis- and transdichlorodiaminoplatinum(II), respectively. The
former is the known anti-cancer agent cisplatin,
whereas the latter has no therapeutic use (3).
The second class of stereoisomers are the socalled enantiomers (from the Greek word for
opposite). The two molecular species of a pair
of enantiomers differ from one another only in
that they are non-superposable mirror images.
From general symmetry considerations, it can
be deduced that molecules which have neither
planes of symmetry nor an inversion centre show
enantiomerism (higher order so-called improper
rotation axes must also be absent).
The Concept of Chirality

Molecules that fulfil the conditions to show
enantiomerism are said to be chiral (from the
Greek word of handedness, a concept introduced by Lord Kelvin in 1893). Molecules,
where the mirror image is identical to the molecule itself are designated as achiral. The two
enantiomers of a pair behave in a chemically
identical way, unless the interacting partner is
also chiral. For example, enantiomers rotate the
plane of incident, linearly-polarised, light of a
certain wavelength by the same angle, but in
102
opposite directions, since such polarised light

can be considered as a pair of enantiomers: one
right- and one left-handed circularly polarised
component.
In general, enantiomers also behave very differently in real chemical reactions, if the reaction takes place between two chiral molecules.
A substance composed of chiral molecules can
occur either as an enantiomerically pure compound (EPC), or as a racemate, which is a 1:1
mixture of both enantiomers, or indeed as anything between these two limits. The enantiomeric purity is nowadays generally given as
the so-called enantiomeric excess (ee), which is
1.0 (or 100 per cent) for an EPC and 0 (0 per
cent) for a racemate.
Many molecules in living systems, such as
amino acids or sugars, but also terpenes, are
chiral and they occur as EPCs. Sometimesthese
naturally occurring enantiomericallypure compounds are referred to as the "chiral pool". It
is unthinkable that biological systems could have
developed without enantiomerically pure compounds, but it is still not completely explainable
how nature achieved the single enantiomeric
occurrence of most chiral compounds during
early stages of evolution.
Racematea
Syntheses of chiral molecules starting from
achiral precursors almost always yield racernates.
A racemate can either crystallise as a macroscopic conglomerate of two kinds of crystals that
themselves are mirror images of each other, or
as uniform crystals where in each unit cell an
equal number of each enantiomer is present.
The latter case occurs more frequently and these
solid phases are called racemic compounds or
racemic modifications. The former case (occurrence of a conglomerate) gave rise, almost 150
years ago, to the discovery of molecular optical activity by Louis Pasteur (4).
Chiral descriptors are needed in order to distinguish between the two enantiomers of a pair.
In principle one pair of symbols would suffice.
For practical reasons, however, several conventions have been established. For organic compounds, the WS convention (so named by Cahn,
Platinum Metals Rev., 1996,40, (3)
Fig. 1 The enantiomeric pair of a M(L"L),

chiral complex; left is A, right is A
Ingold and Prelog) is mostly used (from the

Latin rectus and sinister, respectively), whereas
in co-ordination chemistry the N A designation
is often applied to right- or left-handed helical
chiral molecules.
Using symmetry considerations,Alfitd Werner
had already predicted, in a paper published in
1899, that some types of octahedral co-ordination compounds should be chiral and hence,
in principle, separable into enantiomeric compounds (5). In 1911, the first report of such a
successful separation was published (6).
Platinum Group Metal

Co-ordination Sphere
The co-ordination sphere around many of the
platinum group metal centres is octahedral, see
Figure 1. In particular, the octahedral co-ordination spheres of ruthenium(II), osmium(II),
rhodium(III), iridium(II1) and platinum(IV),
yield a large number of chiral complexes of the
classical Werner type, that is M(L"L)3 or
M(L"L)& where L"L are bidentate ligands
and X is a monodentate ligand, such as C1-, etc.
(2). The number of such complexes is almost
limitless, since there are a very large number
of bidentate ligands.
Interesting examples of such Werner-type complexes are the purely "inorganic" ions [PtS,,12and [PtSl7I2-,respectively (7). In these species,
which should be written as [(Pt(S,),]'- and
[Pt(S&S5]", the chelate rings around the central platinum atoms are formed by sulphur atoms
(a chelate ligand is attached to the central atom
through two or more co-ordinating atoms). For
103
Fw 2 c~mputermodel repmaentationofthetwo isomersof a dinucIeareompIex, [(Ru(bpy)&Lqp~]'+

with identical (homoehird), and with opposite chiralitiea (heteroehiral), respectively, at the two
rutheniumcentres. To the left is A,A, to the right is A,A. Here, ruthenium is eoloured red, hydrogen pale blue, carbon grey and nitrogen dark blue
these species and for most other cases of chiral octahedral complexes, the chiralityis a result
of the helical arrangement of the chelate ligands.
The symmetry group of these molecules (D1)
does not contain any mirror plane or inversion
centre, but only three-fold and two-fold rotation axes, see Figure 1.
(iv) EPCs are needed in therapeutic applications of chiral co-ordination compounds, since
enantiomeric purity is nowadays required for
pharmaceutical molecules.
Thus, for all four types of applications, the
platinum group metals constitute co-ordination
centres of prime interest.
Predetermined Helical Chirality
Controlling the Chirality

The control of chirality at the metal centre can
be achieved by various means. First, racemates
can be separated into pure enantiomers which
can then be used as chiral building blocks. This
method has been applied for the synthesis of
dinuclear ruthenium complexes with tris-diimine
co-ordination spheres (8). Such complexes are
the prototypes of species that can be functionalised to yield photochemical molecular devices
(9). In Figure 2 two isomers of the ruthenium
complex [(Ru(bpy)&bpym]'+, where bpy is 2,2'bipyridine and bpym is 2,2'-bipyrimidine, are
shown. The isomers have different stereochemistry; one is a homochiral complex (having the same chirality A,A at both metal centres), and the other is a heterochiral complex
(different chiralities A,A at the metal centres),
built from units which were obtained by classical resolution of a racemate (that is, separation of the two enantiomers).
However, there are two drawbacks to using
enantiomericallypure building blocks obtained
by resolution of a racemate. One drawback is
As already mentioned, the synthesisfrom achiral starting materials yields racemates, except
for some very special cases (2). The two enantiomers are consequently formed in equal
amounts, and applications for which EPCs are
needed therefore require a separation procedure. Enantiomericallypure coordination compounds are relevant for several important applications:
(i) The stereoselective step in enantioselective
catalysis (a multi-billion pound sterling business) often takes place at the metal site.
(ii) Multicentred supramolecular species of
photochemicallyactive coordination unitsoften
give rise to a large number of stereoisomers
(which makes their detailed characterisation
very difficult), unless enantiomerically pure
building blocks are used.
(iii) Enantiopure chiral metal complexes are
potentially interesting species for solid state
applications in non-linear optics (NLO), since
such compounds must crystallise in noncentrosymmetric space groups.
Platinum Me& Rev., 1996,40, (3)
104
Fig. 3 Bis-bidentate ligand, where the two

chelating units are linked by a chiral bridge
the inevitable loss of at least 50 per cent of the

material, if one is only interested in a building
block of a given chirality. The other, even more
severe drawback is the possibility of racemisation (back-transformation to the 5050 mixture
of the two isomers) under certain reaction conditions. The latter effect is especially important
for ruthenium complexes, which are known to
racemise under the influence of light.
A second method, where complete control
of chirality at the metal centre can be achieved
using ligands that are themselves chiral, is therefore to be preferred. A chiral ligand is shown
in Figure 3.
Here, two bidentate chelates are linked by a
bridge that is anchored at the chiralcentres (carbon atoms with four different substituentswhich
were formerly called asymmemc carbon atoms,
nowadays designated stereogenic carbon centres) A and B, respectively. The ligand mole-
cule is QOW a tetradentate chelate, where two

bpy units are permanently connected. The chirality at the metal centre can be predetermined
completely by this method as we have shown,
by designating a ligand, which fulfils these
requirements.
In Figure 3 the helical chirality is A. An inversion of the chiral centres, A and B, leads to A
chirality at the metal centre, whereas the ligand
is not capable of co-ordinating to one metallic
centre with both bpy moieties if only one of the
chirality centres, A or Byis inverted. Since configurations at carbon centres are stable under
most circumstances, inversion does not take
place at all and the chirality at the metal centre is therefore completely fixed.
Chiral Ligands
The first ligand of this type was CHIRAGEN[6], the ligand depicted in Figure 4; the
number in square brackets, for instance [6] in
this case, indicates the nature of the bridge, here
six -CH2- groups.
This type of ligand was called a CHIRAGEN
ligand [6],since it generates chirality at the metal
centre. The original source of the chirality in
CHIRAGEN ligands is in the saturated part
of the molecule, which is derived from naturally
occurring pinene, a chiral pool molecule. The
ruthenium@) complex, [Ru(CHIRAGEN[6])@Mbpy)l2, shown in Figure 5, where DMbpy
is 4,4-dimethylbipyridine3 has been shown to
N\
Fq.4 Two chirally bridged bipyridine units are co-ordinated in a

manner which predetermines the
chirality at the metal centre
Plarinum Metals Rm., 1996,40, (3)
105
Fig. 5 A ruthenium complex where the

chirality at the ruthenium centre is predetermined by the chirality centres in
the ligand. The colour code is the same
asinFigure2
possess the expected A-configuration, if the ligand is derived from (-)-a-pinene. The latter is
a low priced naturally occurring terpene, which
is commerciallyavailablein either configuration
((-)-a-or (+)-a-)in enantiomericpurity of about
80 per cent.
Since only ligands that are homochiral (having the same configuration at both centres A
and Byrespectively) can co-ordinate to one
metallic centre, a considerable chiral amplification is obtained upon complexation, yielding
a species of about 96 per cent enantiomeric

excess. If more expensive pinene derivatives (for
example myrtenal) with high enantiomericpurity
are used, the ee-value (enantiomeric excess)
of the product is very close to 100 per cent.
The methods used for the synthesis of CHIRAGEN ligands are easy to vary (1 0), and consequently ligands for different purposes can
be designed. For example, when osmium is the
co-ordination centre, it prefers a longer bridge
than ruthenium between the bpy units. Thus,
Os(CHIRAGEN[7]), a ligand with a link of
seven -CH2- groups between the two bpy moieties, is more stable than one with only six
-CHr POUPS.
Also the remaining ligands at the metal centre can be varied. For example, in Ru(CH1RAGEN[6])C12the fifth and sixth co-ordination sites are occupied by chloride ligands that
can be easily substituted, see Figure 6.
In Figure 7 a survey is given of synthesised ligands derived from bipyridine and pinene as the
chiral group. With all these ligands chiral octahedral complexes of the platinum metals, so far
mainly of ruthenium(II), osmium(I1) and
rhodium(III), have been synthesised.
Chiral Planar Complexes

Fq.6 A chird buildii block with the CHIRAGEN ligandr Ru(CHIRAGEN[6])Clr. The
CI l i g ~ a Sare green and ruthenium is red
Platinum Metah Rev., 1996,40, (3)
As discussed above, octahedral complexes

(OC-6 complexes according to W A C nomenclature) with two or three bidentate ligands
106
Fig. 7 A selection of chiral

ligands derived from pinene and
b i p y r i h Coqlexea of all these
ligands with platinum group
metals have been prepared
are intrinsically chiral. The d platinum group

metals - rhodium(I), iridium(I), palladium(I1)
and platinum(I1) - form complexes with square
planar (SP-4) co-ordination geometry. A large
number of such complexes has been investigated
and they play an important role as catalysts,
or at least as intermediates in many catalytic
reactions. The SP-4 geometry is inherently achiral, but it can become chiral under special circumstances. This was observed for the first time
in a ligand which has large substituents, as shown
in Figure 8 (1 1). It is noteworthy that the strong
trans-influence of the carbon-bonded ligand
always directs these ligands into the cisposition.
Achiral ligands, such as those shown in Figure
8, again of course, yield racemates. The same
type of synthesis that produced the pinene derivatives of bipyridine, shown in Figure 7,can be
used to obtain cyclometallating ligands (with
CANco-ordination). In this case predetermination of the chirality at the metal centre is
achieved. For example, in the complex shown
in Figure 9, where the ligand is chiral owing to
the pinene substituents, chirality is predetermined at the metal centre (12). The chirality of
the complex can again be described by the
Platinum Me& Rev., 1996,40, (3)
descriptors used for octahedral complexes,

because the two ligands form a two-bladed helix.
In Figure 9, the A-form of the complex is
depicted.
Oxidative Addition Reactions

There are many possible reactions for these
types of complexes. Oxidative addition is one
interesting type of reaction that square planar,
SP-4,platinum(I1)-compounds undergo. Here
the oxidation number of the metal is increased
from +I1 to +IVYand simultaneously, the coordination number changes from four to six,
yielding again an octahedral species. In the case
of SP-4 complexes with predetermined chirality at the metal centre, an octahedral species is
obtained which preserves the chirality in the
resulting bis-bidentate OC-6 complex (12).
Conclusions
A large number of chiral octahedral and a few
chiral square planar complexes of the platinum metals have been known for a long time.
These complexes have hitherto always been prepared as racemic compounds. A newly developed synthesis of pyridine and bipyridine ligands with attached groups derived from
107
Fig. 8 A two-bladedhelix is formed by s t e r i d y demandq ligands in quare planar platinum

complexea. Platinum ie pink here
naturally occurring terpenes, such as pinene or molecular devices, as materials with interesting
carene, leads to chiral ligands, and these direct non-linear optical properties and finally as
the chirality at the metal centre into a prede- chiral pharmaceuticals.
termined configuration. Thus, in many
instances, only one helical form of the complex Acknowledgements
This paper describes a small selectionof results prois obtained.
duced by teamwork. Thanks are due to Dr P. Hayoz,
Potential applications for such platinum group who introduced the synthesis of the terpene derivametal species lie in the field of enantioselec- tives of pyidine ligands,and also to Profasor P. Belser,
Dr N. Fletcher, Dr X. Hua, Dr S. Rupprecht, Dr E.
tive catalysis, the design of stereochemically Jandrasics,H. R Miirner, M. Gianini,M. Riwin, Ph.
well-defined large functionalisedstructures for Collomb, M. Ziegler and B. Kolp.
Fig. 9 A qmre-plannrcomplex of platinum(II)r on the left in red, the pinene parte of the ligan&, which are responsiblefor the chirality (A in the p-t
awe) at the metal centre; on the right,
platinum i E not visible, sdphnr atom are yellow with the lone pairs in pde pink
Platinum Met& Rev., 1996,40, (3)
108
References
8 X.Hua and A. von Zelewsky, Inorg. Chem., 1995,
1 A.Werner, Z. Anorg. Chem., 1893, 3, 267

2 A. von Zelewsky, Stereochemistry of
Coordination Compounds, JohnWiley and Sons
Ltd., London, 1996
3 Metal Compounds in Cancer Therapy, ed. s.
P. Fricker, Chapman and Hall, London, 1994
4 L. Pasteur, Ann. Chim., 1848,24,459
5 A.Werner and A. Vilmos, Z. Anorg. AIlg. Chem.,
1899,21, 145
6 A. Werner, Chem. Ber., 1911,44, 1887
7 P. Cartwright, R.D. Gillard, R. Sillanpaa and J.
Valkonen, Polyhedron, 1987,6, 1775
34~
5791
9 V. Balzani and F. Scandola, Supramolecular
Photochemistry, Ellis Horwood, 1991,New York
10 P. Hayoz, A. von Zelewsky and H. Stoeckli-Evans,
3 A m . Chem. SOC.,1993,115,5111;P.Hayozand
A. von Zelewsky, TetrahedronLen., 1992,33,5165
1 1 C. Deuschel-Cornioley, H. Stoeckli-Evans and
A. von Zelewsky, J. Chem. SOC.,Chem. Commun.,
1990,121
12 M. Gianini,A.Forster, P. Haag, H. Stoeckli-Evans
and A. von Zelewsky, h o r g Chem., 1996 to be
published
Palladium Facilitates Optical Switching

HYDROGEN ADSORPTION ALTERS PROPERTIES OF RARE EARTH FILMS
Hydrogen gas can permeate palladium, diffuse through it and be stored in it. This property has been known for many years, and has
been discussed in this journal on numerous occasions; see (1-3) and references therein. Similarly,
the effects resulting from the alloying of palladium with rare earth metals have been reported
here (4). Now, physicists at Vrije University in
The Netherlands have combined these properties to produce thin yttrium and lanthanum
films coated with palladium, which display an
optical switching phenomenon as they adsorb
hydrogen (J.N. Huiberts, R. Griessen, J. H.
Rector, R. J. Wijngaarden, J. P.Dekker, D. G.
de Groot and N. J. Koeman, Yttrium and
Lanthanum Hydride Films with Switchable
Optical Properties, Nature, 1996,380, (657 l),
23 1-234).
Thin films of yttrium and lanthanum (500 nm)
were evaporated under UHV and then coated
with a thin layer of palladium (5 to 20 nm). The
palladium film acts as a support for the films,
forms an oxidation barrier, and allows hydrogen to permeate through and be adsorbed by
the rare earths. It also enables various physical
properties to be measured.
Films were examined by electrical resistivity
and light transmission measurements. At the
start of the experiment hydrogen, at room temperature and 0.9 x lo5Pa pressure, was introduced into the apparatus and began to diffuse
through the palladium overlayer. The yttrium
film adsorbed hydrogen and changed to yttrium
hydride, YH,, which remained metallic up to
x 2, but as more hydrogen was adsorbed, the
YH, changed to a semiconductor, corresponding to Y H Z . 8 6 .
The films also undergo optical changes as
hydrogen is taken up. After 17 seconds of expo-
Platinum Metals Rev., 1996, 40, ( 3 )
sure to hydrogen, an initially perfectly reflecting yttrium film, begins to precipitate the dihydride phase, with resistivity 5 times lower than
that of pure yttrium. After 65 seconds the resistivity increases rapidly and for a few seconds
there is increased optical transmission, shown
by a partially reflecting film, close to the dihydride composition. As hydrogen adsorption
increases, optical transmission drops to zero,
but after 80 seconds there is an abrupt and drastic increase in the optical transmission intensity, shown by a non-reflecting, transparent yellow film. This corresponds to YH2.86to the
trihydride, YH,.
For a lanthanum-palladium film the pattern
is similar, but without the transparency window
which occurred around 67 seconds; optical
switching in LaH. is more gradual than in YH,.
Thus, there is a continuous, reversible metalinsulator transition in thin yttrium films supported and protected by a palladium overlayer,
which can be brought about at room temperature by changing the hydrogen pressure, between
hydrogen : yttrium ratios of 1.8 and 2.9. As
hydrogen pressures increase, the films change
from a reflective, shiny, mirror-like state to a
yellow transparent state.
It is suggested that this technique could be
used to investigate other rare earth films which
undergo similar changes, and that such a significant optical phenomenon might find wide
technological applications.
References
F. A. Lewis, K. Kandasamy and B. Baranowski,
Platinum Metals Rev., 1988, 32, (l), 22
2 F. A. Lewis, op. cit., 1994, 38, (3), 112
3 J. E.Philpott, op. cic., 1985, 29, (l), 12
4 M.L.Doyle and I. R. Harris, op. cic., 1988, 32,
(31, 130
109
Emission Control Technology

PROGRESS REPORTED AT THE SPRING SAE CONFERENCE
It was unusually warm during the traditional
end-of-February Congress of the Society of
Automotive Engineers (SAE), held this year flom
24th to 27th February - there was no snow on
the downtown Detroit streets! This Spring conference is the major, general SAE conference
covering all aspects of automotive engineering,
with over 47,000 delegates attending this year.
Fine weather and a broad range of interesting
papers concerned with exhaust after-treatment
made this a memorable event for those concerned
with emissions control, and the continuing
importance of developments in this area was
reflected in the high attendance at the sessions.
Space prevents a review of all the relevant
papers, so a selection has been made to illustrate the direction catalyst technology is taking in response to increasingly stringent legislation on emissions. Reference numbers of the
original papers are given in parentheses.
Autocatalyst formulations have become more
complex over recent years and may, for example, involve separated platinum metals each with
an optimal promoter package. A paper by
Degussa (960802) gave some insight into the
design of such formulations, and a comprehensive study by Volvo (960801) of reactions
over a double-layer trimetal (platinum-palladium-rhodium) catalyst enabled a dynamic
kinetic model to be developed, which included
sulphur dioxide effects.
Solving the Cold Start Problem

Starter Catalysts
Reduction of emissions during the cold start

period is the key objective for meeting future
regulations, and the use of low temperature lightoff catalysts mounted close to the exhaust manifold to decrease warm-up time is an attractive
approach for achieving this. However, operation
in this position demands particularly good thermal durability of the catalyst. Space constraints
often preclude location of large volume closecoupled catalysts near the exhaust manifold, and
Platinum Metals Rev., 1996,40, (3), 110-1 11
combinations of a small close-coupled starter

catalyst with a larger underfloor unit can provide
an effective system.
Toyota (960797) explored the effectiveness
of such two-catalyst systems, and Johnson
Matthey (960799) demonstrated that both the
U.S.A.LEV/ULEV and European Stage 3 standards can be met with suitable high-activity
catalysts of good thermal durability.
The attainment of low emission levels depends
on rapid warm-up of the front catalyst and the
presence of a sufficientlylarge total catalyst volume to maintain performance under normal
operating conditions. Audi (960261) stressed
the roles of engine management in rapid heating, and secondary air injection to enhance catalyst light-off. Starter catalyst performance
depends on several parameters: a small volume
heats up quickly, but a larger volume produces
a greater exotherm (temperature rise), and this
is reflected in the accumulated hydrocarbons
emissions during a test cycle. Starter catalyst
cell density also affects performance: there is a
monotonic improvement as it increases.
However, when a starter catalyst is combined
with an underbody catalyst the system performance is less dependent on the characteristics
of the starter, provided that it quickly gives a
sufficient exotherm to light-off the main
catalyst.
Metallic monoliths have typically been used
in starter applications, and Corning (960262)
reported a comparison of ceramic and metal
foil-based starter catalysts. From their tests, they
concluded that with the same outside diameter
and back-pressure characteristics similar emission and durability performance can be obtained.
Corning (960349) and NGK (960565) reported
additional thermal durability results for ceramic
monoliths in close-coupled locations. The latter proposed a design using a dual cone structure for both the converter inlet and outlet to
minimise heat conduction, thus decreasing the
temperature of the surrounding mat and
110
lowering the surface temperature of the converter to below 45OOC - when the catalyst itself
is at a temperature of 1050C.
Electrically Heated Catalysts

An alternative approach for reducing cold start
emissions is to preheat electrically a small platinum group metal containing catalyst in front
of the main catalyst. High electrical power
requirements have tended to inhibit adoption
of this concept, but the first electrically heated
catalyst (EHC) application was described by
Alpina/BMW and Emitec (960349), and it is
interesting to note that, on the car which they
describe, the power is switched between two
EHCs on either side of the engine in order to
minimise power consumption.
Emitec (960339) presented a separate paper
on the general applicability of foil-based EHCs,
and W. R. Grace (960341) also presented system performance with related EHCs. Honda
(960342) compared foil-based and extruded
EHCs in vibration, heat impact and distortion
durability tests, and discussed the use of battery
and alternator power supplies. They opted for a
special alternator. In contrast, Hyundai (960350)
investigated characteristicsof both conventional
lead/acid and nickeymetal hydride batteries for
supplying EHC current, and concluded that the
latter has significant attractions - as lead/acid
batteries do not sustain the necessary heavy currenddepth of discharge over many cycles.
NGK (960340) gave details of the design concepts and durability data of extruded metal
EHCs and Corning (960345) presented vehicle durability results for their latest EHC design.
Clearly, EHC-based technology has been developed to a stage where it could be used in series
production, but it appears that in practice passive starter catalysts are more favoured, due to
their not needing associated equipment.
Lean-Burn Technology
Catalysts for lean-burn engines are likely to
become increasingly important; a concern here
is NOx reduction in the presence of excess oxygen. Orbital (960361) highlighted the fact that
extremely lean operation of a direct injection
stratified charge two-stroke engine results in

inherently low NOx levels, while Degussa
(960133) showed how zeolite can be used to
store and activate hydrocarbons in diesel engine
exhaust during the start-up phase. This improves
NOx reduction. Corning (960343) described
a by-pass system (two conventionalceramic platinum group metal catalysts and an adsorber)
in which zeolite is used to absorb hydrocarbons
during the cold start of a conventional gasoline
engine. They also described (960348) an in-line
adsorptionsystem which uses a flow of air to prevent exhaust gas passing through a central bypass in an adsorber monolith during start-up.
Developments in Sensors
Sensors are important for the correct operation of emission control systems. Oxygen sensors are used to maintain accurate air/fuel ratios,
and in the future it seems likely that other types
of sensors will be needed. Several reports were
concerned with other sensors: Matsushital
Panasonic described (960336) a wide range thermistor for exhaust gas temperature measurement. NGK reported a new high performance
platinum resistive temperature sensor (960333),
and discussed its possible use in on-board diagnostic applications in which the predicted temperature rise on a catalyst is compared with the
corresponding measured increase.
Another NGK paper (960334) described a
new NOx electrode; this multi-layer zirconia
system, operating at 600 to 7OO0C,involves oxygen pumping with platinum electrodes and, in
a separate zone, dissociation of nitric oxide takes
place over porous rhodium. The oxygen formed
is measured with an oxygen electrode, and the
concentration is found to be proportional to the
amount ofNOx originally present. Gold is used
to inhibit nitric oxide dissociation on platinum
electrodes, and to improve off-set current
characteristics.
Thus, once again the SAE conference has highlighted the key role played by the platinum group
metals in emission control technology, and has
demonstrated the amount of worldwide effort
and expertise committed to improving the performance of emission control systems. M.V.T.
111
Electronic and Nuclear Magnetism in

Platinum-Iron at Ultralow Temperatures
LOW TEMPERATURE WORLD RECORD ESTABLISHED
By W. Wendler, T. Herrmannsdorfer,*S. Rehmann

and E Pobell**
Physikalisches Institut, Universitat Bayreuth, Germany
I n Februarx 1996, physicists at the University of Bayreuth claimed a world
record for producing the lowest temperature yet achieved when they announced
the results of their work with platinum. They cooled 31.4 grams of platinum
to 2 millionths of a degree Celsius above absolute zero temperature, -273.15"C.
I n this paper they describe the theory and the practical work behind this accomplishment. Research in low temperature physics involves the construction of
detailed and precise knowledge of the atomic and nuclear structures and their
interactions in atoms. Some effects due to atomic and nuclear structure, particularly magnetic effects, are only seen at very low temperatures; however their
effects have consequences a t higher temperatures, although these are not
usually observed. T h u s , this and other low temperature work is contributing
to a fundamental understanding of the magnetic behaviour of materials.
The study of magnetism is one of the most
interestingfields in solid state physics. Electronic
magnetism shows a wide spectrum of different ordering phenomena at temperatures from
about lo3 K, where the ferromagnetic phase
transition in iron occurs, to about 10.' K, where
Ce3+ions in the paramagnetic salt CMN order
magnetically. (CMN is cerium magnesium
nitrate. ?C.c''NO;) 3.3Mg(N03)2.24H20,
which
previously found application for electronic
demagnetisation refrigeration before 'He-'He
dilution refrigerators were used (1). Nowadays
some research groups use it for thermometry at
mK temperatures, but we used a PdFe thermometer in this temperature range).
Interacting magnetic moments of localised
electronic shells or itinerant electrons are responsible for phenomena such as ferro-, ferri-, antiferro- and meta-magnetism or spin glass freezing. However, many elements and compounds
do not contain such electronic magnetic
moments, but very often their nuclei carry a
*Hahn-Meitner-Institut Berlin, Berlin, Germany
.* Forschungszentrum Rossendorf, Dresden, Germany
Platinum Metals Rev., 1996, 40, (3), 112-1 16
magnetic moment due to the nuclear spin. Since

nuclear magnetic moments are three orders of
magnitude smaller than their electronic counterparts, and as the interaction energy is proportional to the square of the magnetic moment,
ordering phenomena in the nuclear spin system
are expected to occur only in the microkelvin
temperature range or at even lower temperatures.
Apart from solid 'He with its strong quantummechanical direct exchange force, and the Van
Vleck paramagnets with hyperfine enhanced
magnetic moments, one has to distinguish
between two groups of nuclear spin systems:
those in insulators and metals with a
coupling between the nuclei and the conduction electrons, and
those in metals with a strone: coupling
between the nuclei and the conduction
electrons.
The Korringa constant, K, is an important
parameter to characterise the strength of this
interaction. The Korringa constant is given by
the conduction electron temperature, T.~rcr,o.,
.
.
112
multiplied by the spin lattice relaxation time, zI. temperatures of a few mK at concentrations of
For the first group of materials, the Korringa ppm (5). This system of randomly distributed
constant is larger than 1 Ks. As the spin lattice electronicmagnetic moments may have a strong
relaxation time zI becomes very long at tem- influence on the nuclear magnetic properties.
peratures below 1 mK (zl > 1000 s), it is possible to cool only the nuclear spin system to Searching for Nuclear Magnetic
nanokelvin or even picokelvin temperatures for Ordering in Platinum
In order to search for a possible nuclear maga time long enough to perform nuclear magnetic
ordering of 195Pt
and to study the above
netic investigations,while the conduction elecmentioned
interaction
between
nuclear and electrons stay at a much higher temperature (Tekmm
tronic
magnetism,
we
have
investigated
plat> 100 pK). For systems such as these, nuclear
magnetic ordering phenomena have been inum samples containing magnetic impurities
observed in silver (K = 12 Ks, T, = 0.6 nK) and at concentrations of 11 and 4 1 ppm. The impurities were mainly iron, carrying an electronic
copper (K = 1.3 Ks, T, = 60 nK) (2).
However, it is much more difficult to observe magnetic giant moment of eight times the
Am). The
nuclear magnetic ordering phenomena in the Bohr magneton pB (pB= 9.274 x
second group, since in this case, the whole sys- properties that we measured were:
heat capacity in magnetic fields, B;
tem has to be cooled because of the strong cou(0 & 0.05) mT IB I248 mT
pling between the electrons and the nuclei. On
AC susceptibility at B = (0 f 0.05) mT and
the other hand the indirect exchange interacnuclear magnetic resonance a t fields
tion between nuclei in these systems is stronger
2.5 mT I B 122.8 mT.
than the dipole-dipole interaction, and thereMeasurements were taken at temperaturesT w
fore ordering phenomena are expected to occur
t 0.3 pK and T,I,,~,2 2 pK, the latter being
at temperatures of up to tens of microkelvin.
the lowest temperature to which electrons and
phonons of a material have ever been reftigerated.
Work with Platinum as a
.
..
Strong Coupling System

Recently, we have been able to observe a
nuclear ferromagnetictransition of this type with
the 113151n
nuclei in AuInz (K = 0.1 1 Ks) at a
temperature of 35 pK (3). Another very interesting material in this group is platinum, which
has a very small Korringa constant, of size only
K I0.03 Ks. The nuclear magnetic moment of
195
Pt is a factor of 10 smaller than that of the
indium nuclei and only 33.8 per cent of the platinum nuclei carry the rather small magnetic
moment of 0.597 p (nuclear magneton p,, =
5.05 x 10. Am). Therefore, it is necessary to
reach temperatures below 1 pK to observe
nuclear magnetic ordering in platinum (4).
The additional interest in platinum comes from
the fact that electronic magnetic 3d impurities, such as iron, form so-called giant moments
in this strongly enhanced electronic Pauli paramagnet. (Platinum and also palladium are both
strongly exchange enhanced Pauli paramagnets.)
The giant moments show spin glass freezing at
Platinum Metals Rev., 1996,40, ( 3 )
Lowering the Platinum Temperature

The ultralow temperatures that are necessary for these experiments were obtained by
using the adiabatic nuclear demagnetisation
technique. First, 17 kg copper were precooled
in the Bayreuth nuclear demagnetisation refrigerator (6) (6.5 kg in an external field of 8 T )
by a commercial He-*He dilution refrigerator
to a temperature of 11 mK.
Then, after a thermal decoupling of the copper nuclear refrigeration stage from the mixing chamber of the dilution refrigerator, the
external magnetic field was slowly reduced. At
the end of this process the copper stage reached
temperatures of about 50 pK. The platinum
sample (n = 161mmole of weight 3 1.4 grams)
was exposed to a magnetic field of 0.37 T and
thermally connected to the copper stage via a
superconducting aluminium heat switch. The
platinum was then precooled, by the copper
stage, to a temperature of approximately 100 pK.
113
Fig. 1 Heat capacity of BFe.

samples, where z = 41 ppm and
11 ppm, in fields of:
(a) 248 mT,
(b) 22.8 mT,
(c) 2.5 mT for z = 11 ppm and
0 mT for z = 41 ppm.
The solid lines represent the
behaviour of platinum in the
nuclear paramagneticstate. The
dashed liner are calculated
assuming a spatially varying
internal field, caused by the iron
impurities
'O-5-4
TEMPERATURE,
mK
Subsequently, the platinum stage was thermally

decoupled from the copper stage and the field
was reduced. Eventually, in external fields of
B 5 0.05 mT, the temperature of the nuclear
spin system of platinum reached 0.3 pK. In these
fields (B 5 0.05 mT) the temperature of the
nuclei, Taw&,,
was lower than the temperature
of the conduction electrons, Tebcmn.
If the adiabatic demagnetisation was stopped
at somewhat higher fields, for example 2.5 mT,
nuclear temperatures of (0.8 f 0.2) pK could
be measured directly after demagnetisation.
Taking the measured heat leak of (12 f 2) pW
into the platinum sample into account and the
measured Korringa constant K = (7 f 3) mKs
for platinum in these fields, the temperature of
Platinum Metah Rev., 1996, 40, (3)
the conduction electrons has to be below 2 pK.

During the next three hours after finishing the
demagnetisationthe conduction elecuons stayed
below 3 pK. The small value of 7 mKs for the
Korringa constant, in contrast to its literature value
of 30 mKs, is caused by magnetic impurities.
Measurement of the Platinum Temperature
The temperature of the platinum was determined from the magnetisation of its nuclear spin
system, using pulsed nuclear magnetic resonance
(NMR) in fields B 2 2.5 m T and the AC susceptibility technique in fields B = (0 f 0.05) mT.
At temperatures of 2 20 pK the NMR signal was
calibrated against an independent platinum-wireNMR thermometer, which is itself calibrated
114
0 08
0 06
>
004
U
VI
3
VI
0 02
I
10-4
10-
10-2
10-1
100
101
TEMPERATURE, mK
Fig. 2 AC susceptibilities (f = 16 Hz) of the two RFe, samples. The solid lines at temperatures
T > T,(T,are the spin glass freezingtemperatures) show the Curie behaviour of the electronic magnetic impurities. The Curie constantsare determined in a SQUID magnetometer at 1.6 K IT 5 40 K
and are used to calibrate the data to obtain absolute values of susceptibility. The solid lines at
T C 50 pK show the Curie behaviour of the '"Pt nuclei which is used to derive the temperaturescale
at T < 20 pK in zero field
against the paramagneticsusceptibility of a PdFex

sample at temperatures T 2 10 mK (1).
For the temperature calibration we assume
that the magnetisation, detected by the NMR
signal and the measurement of nuclear AC susceptibility, follows a Curie law
llTnw~o,)
at
low polarisation. If it follows a Curie-Weiss law
(x l/(Tmuba,-On)),
we would have to correct
our temperature scale by 0.(see below).
The measured heat capacity data of the two
PtFe, samples in different magnetic fields is
shown in Figure 1. The solid lines show the
nuclear paramagnetic behaviour. In a magnetic
field of 248 mT, there is a good agreement at
T I 1 mK. However, at higher temperatures the
measured heat capacities are larger than expected
and scale with the impurity concentration. At
lower fields, such as 22.8 mT, this effect is much
more pronounced, and at 2.5 mT or in zero field
(x -
Platinum Metals Rev., 1996, 40, (3)
we observe an enhanced heat capacity over

almost the whole temperature range. This effect
can be described by a spatially varying internal field caused by the electronicmagnetic impurities, assuming that this field behaves in a similar way to the electronic polarisation cloud in
the conduction electron system -which forms
the giant electronic moment. The dashed lines
in Figure 1 are calculated using only two fitting
parameters. There is a good agreement with the
measured data. Therefore, we are able to
describe the internal field in platinum as being
due to electronic magnetic impurities.
Does Platinum Have

Nuclear Magnetic Ordering?
In order to search for a nuclear magnetic ordering transition in platinum, we have measured
the nuclear and electronic AC susceptibilities
115
of the two platinum samples in an external field

B 5 0.05 mT. The results are shown in Figure
2. The two maxima at millikelvin temperatures
are caused by the spin glass freezing of the
magnetic 3d impurities in platinum at freezing
temperature, Tj. At temperatures T > Tjthe AC
susceptibilityshows Curie behaviour with Curie
constants CIlm= 122 pK and C41,m= 448 pK,
determined at 1.6 IT I 40 K in a commercial
SQUID magnetometer.
We used this known behaviour (5) to scale our
measured data in units of differential volume
susceptibility. At T < Tj the susceptibility
decreases linearly with temperature and increases
again a t T < 0.1 mK. The latter increase is
caused by the nuclear paramagnetic behaviour
of the Pt nuclei with a Curie constant of
CR = 0.0 185 pK. No maximum in the susceptibility was found and therefore no evidence for
nuclear ordering in our samples could be

detected down to the minimum nuclear
temperature reached of 0.3 pK.
Conclusions
The temperatures achieved in our platinum
samples, for the conduction electrons and
phonons, which are below 2 pK, are the lowest temperatures ever reached in equilibrium.
No evidence of nuclear magnetic ordering in
platinum could be detected. This shows that the
temperatures achieved were still measured in
the nuclear paramagnetic state where the Curie
(or Curie-Weiss) law is valid, and therefore our
determination of temperature, assessed via this
law is correct.
This work should aid in extending understanding of the interplay between electronic and
nuclear magnetism at very low temperatures.
References
F. Pobell, Matter and Methods at Low 4 P.Kumar, J. Kurkijarvi and A. S. Oja, Phys. Rev.
Temperatures, Springer Verlag, Berlin,

Heidelberg, 1992
2 A. S. Oja and 0. V.Lounasmaa, to be published
in Rev. Mod. Phys., 1996, July
3 T. Herrmannsdorfer, P. Smeibidl, B. SchroderSmeibidl and F. Pobell, Phys. Rev. Len., 1995,74,
1665
B, 1986,33,444
T. Herrmannsdorfer, S. Rehmann, W. Wendler
and F. Pobell, to be published in J. Low Temp.
Phys., (1996)
6 K. Gloos, P. Smeibidl, C. Kennedy, A. Singsaas,
P. Sekowski, R. M. Mueller and F. Pobell, J. Lo4u
Temp. Phys., 1988, 73, 101
5
Palladium Colloid Catalvst Used in Microcontact Printing

J
There are several methods in current use for

transferring very fine patterns onto substrates
for printed electronic circuitry. These all involve
the selective metallisation of the area to be
treated and use various techniques, such as photolithography or electroless plating. However,
scientists at Harvard University have now
announced a new method of electroless deposition, which they have demonstrated with copper but suggest could also be used for the deposition of other metals (P. C. Hidber, W. Helbig,
E. Kim and G. M. Whitesides, Microcontact
Printing of Palladium Colloids: Micron-Scale
Patterning by Electroless Deposition of Copper,
Langmuir, 1996, 12, (3,
1375-1380).
Their new strategy involves the manual transfer of a palladium colloid catalyst onto a substrate surface by microcontact printing (pCP);
this uses a patterned elastomer stamp made from
poly(dimethy1siloxane). The stamp is previously
dipped into the palladium colloid, which has
been stabilised with tetraalkylammonium
bromides. This is followed by the electroless

deposition of copper which proceeds by immersion of the substrate in a copper plating bath,
and occurs only at the regions coated with the
palladium colloid, where a catalytic reaction
occurs.
Copper lines of micron and submicron widths,
having edge resolution of 100 nm, were produced on a variety of substrates, including glass,
silicon with a silicon dioxide layer, and polymers. Both flat and curved surfaces can be plated
without loss of resolution. In addition, freestanding, flexible structures can be produced
by dissolving the substrate when the metal film
reaches the required thickness or by allowing
the internal stress in the electroless copper layer
to exceed the adhesion strength, when delamination occurs.
While films of approximately uniform thickness can be produced by this method, ways of
obtaining structures which have different layer
thicknesses have also been developed.
116
Platinum and Biological Systems

Metal Ions in Biological Systems, Volume 32: Interactions of Metal Ions with Nucleotides.
Nucleic Acid, and Their Constituents
EDITED BY ASTRID SIGEL AND HELMUT SIGEL, Marcel Dekker, New York, 1996, 848 pages,
ISBN 0-8247-9549-0, U.S.8225.00
Nucleotide- and nucleic acid-metal ion interactions have been a major focus of research for
over forty years. Many of the enzymes involved
in RNA and DNA biochemistry utilise metal
ions. Metal ions affect the stability of the three
dimensional structures of nucleic acids and
nucleic acid-protein complexes, and indeed, the
platinum-based anticancer drugs exert their
effect by interaction with DNA. This volume
and Volume 33 (to be reviewed in a future issue)
bring together international experts who review
the present status of research in this field.
The book can be subdivided into four sections,
with the first ten chapters covering the interaction of metal ions with the low molecular
weight nucleotides. Chapters 11 to 15 review
interactions with high molecular weight ligands,
such as nucleic acids and nucleic acid-protein
complexes. These chapters provide the background for two chapters on the role of metals
in gene regulation. The final chapters examine the interaction of the platinum anticancer
drugs with nucleic acids.
Interactions of naturally occurringmetals (with
biological systems) are a key feature of this volume, and though not of direct relevance to this
journal, their significance should not be overlooked. The chapters on gene regulation are
at the leading edge of an important area in
modern inorganic biochemistry.
The platinum group metals feature strongly
throughout the book. The interactions of metal
ions and nucleic acids can be studied in the solid
state using X-ray diffraction, or in solution using
techniques such as NMR or UV-Visible spectroscopy. The use of platinum complexes as
probes for these techniques forms sections in
Chapters 4,6 and 11. In Chapter 3,R B. Martin
describes the use of palladium complexes to provide the empirical basis for a discussion of metal
ion binding to purines. In Chapter 9, T. Rau
Platinum Metals Rev., 1996,40, (3), 117
and R. van Eldik, and in Chapter 10, J.

Arpalahti, describe the kinetics of palladium(I1)and platinum(I1)-nucleobase interactions.
An important reason for studying metal-DNA
interactions is to understand the mechanism of
the platinum anticancer drugs. A review of the
current status of structure-activityrelationships
of platinum anticancer drugs, is presented by
N. Farrell in Chapter 18, focusing on recent
work on the biological activity and unique DNA
interactions of truns-platinum complexes, previously thought not to have activity as anticancer
drugs. In Chapter 19, M. J. Bloemink and J.
Reedijk review the mechanism of cisplatin binding to DNA from both a structural and a kinetic
perspective, and discuss the significance of this
for new platinum complexes.
The still unanswered question of how cisplatinDNA binding leads to tumour cell death is
addressed by J. P.Whitehead and S. J. Lippard
in Chapter 20, who describe the current understanding of the repair of platinum lesions on
DNA. They discuss the binding of a DNA damage-recognition protein, leading to the formation of a platinum-DNA-protein ternary complex, and its involvement in platinum-induced
cell death. Since the discovery of cisplatin many
laboratories have attempted to identify other
metal-based anticancer drugs, and in Chapter
2 1,M. J. Clarke and M. Stubbs discuss the interaction of experimental ruthenium and rhodium
metallopharmaceuticals with DNA.
Metal ions play an important role in many biological processes - the rationale for this long running series. This is an excellent book and maintains the high standards set by this series. There
are occasional overlaps between chapters, perhaps only to be expected in such a long book;
however, this is offset by the quality and topical
nature of the conmbutions, making this a valuable addition to bioinorganic literature. S.P.F.
117
Hydrocarbonylation in Platinum
Metals Metallurgy
By Professor I. Y Fedoseyev
Kaluga Branch of the Moscow State Technical University, Kaluga, Russia
For manyyears we have been studying the reactions of carbon monoxide with
chlorocomplexes of the platinum metals in various solutions, such as hydrochloric acid. These hydrocarbonylation reactions result in the formation of various
platinum metals carbonyl complexes. Hydrocarbonylation has been used to
extract the platinum group metals from the anode muds which remain after
the production of copper and nickel. The processes involved, which are described
below, produce no waste and therefore do not require special reagents or apparatus. This makes their use very effective for the metallurgy of the platinum
group metals. I n this paper we discuss the general results of these investigations and some of their applications, such as in the production ofpowders
and catalysts, for which the hydrocarbonylation process is suitable.
We have been studying the extraction of platinum group metals from the anode mud residues
which remain after copper and nickel have been
extracted from mineral mined in the nickel-copper sulphide deposits at Noril'sk in the Arctic
Circle in North Russia ( 1).
Carbon monoxide is known to react in solution with platinum metal chlorocomplexes.The
redox reactions which take place are:
CO
+ HzO = CO2 + 2H' + 2e-
M"' + xe- = M"-"
(0
(ii)
where M is a platinum group metal.

This results in the production of lower valency
carbonyl chlorides, carbonyls or metals. The
combination of reactions (i) and (ii) is a hydrocarbonylation process of which the kinetics and
reaction mechanism are already well known.
The rate of the reaction of carbon monoxide
with solutions of chlorocomplexes of the platinum group metals takes place in the following order:
Pdn > Pt' > Pt" > Rh"' > Ru" > = 0s" >> Irw
However, there is only limited information

available about various technological aspects of
the process (2-6). The utilisation of the hydrocarbonylation reaction (for extraction of the plat-
Platinum M e &
Rev., 1996,40, (3), 118-125
inum group metals) depends on characteristic

properties of carbonyl complexes and involves:
a redox decomposition with formation of
the corresponding metal
extraction of carbonyl complexes in the
organic phase
formation of insoluble substances
a sorption process
Selective Concentration of Platinum

Group Metals from Anode Muds
The main metals produced in the Noril'skTalnakh region within the Arctic Circle in Russia
are copper, nickel and the platinum group metals. Noril'sk lies on the northwestern edge of
the Siberian platform and is the main source of
the platinum group metals in Russia, the other
production area being a t Pechenga near the
Finnish border, and the city of Murmansk in
the Kolskiy Peninsula.
After copper and nickel have been extracted
the anode muds still contain non-ferrous metals and noble metals. The technology for processing copper-nickel muds has many stages
including burning, smelting and electrolysis,
and as a result, the platinum metals are distributed among three concentrates, which also
contain many non-ferrous metals. One of the
118
Initial solutton
Carbon monoxide
concentrate-1 P t , Pd. Au. Ag. Se, Te
Rh, Ru, I r and non-ferrous metals
Water phase
Extraction
*I
Organic phase
Obtaining non-ferrous metals
e3-J
,
Re-extraction
w a t e r phase
Organic phase
Obtaining concentrate
-TI' Rh. R u , I r
The principles of the hydrocarbonylation process for obtaining concentratesof the noble metals
concentrates has, for example, the following

composition, in per cent: palladium 35 to 45,
platinum 15 to 20, rhodium 0.4to 0.6, ruthenium 0.08 to 0.15,iridium 0.04 to 0.06, silver
8 to 10, copper 0.7 to 2.5, nickel 0.6 to 2.5, iron
1.5 to 4.0,sulphur 3 to 5, selenium 1 to 1.7and
tellurium 1.5 to 2.5.
Hydrocarbonylation is the principle technology which is then used for obtaining concentrates of the platinum group metals from solutions of anode muds. Such solutions can be
prepared, for example, from the copper and

nickel anode muds by the action of chlorine gas,
or by addition of hydrochloric acid.
The principles of the hydrocarbonylation
process are shown in the Scheme, and the
processes were used in our laboratory with copper and nickel anode mud solutions produced
by the Noril'sk Nickel Combine, which is the
only mining and metallurgical works in that area.
The hydrocarbonylation process, used for such
complex anode mud solutions, conforms to the
Table I
Distribution of Noble Metals Produced from the Copper Anode Mud Solution
Using the Hydrocarbonylation Process
I
Metal
Concentrate-I
Pd
Pt
Rh
Ru
Ir
Metal distribution, in per cent, from the initial amount
Au
Ag
99.97
98.32
103.90
none
none
100.40
98.25
Washings
Organic
phase
0.42
1.69
none
7.63
none
none
none
0.03
0.03
1.15
73.00
1 15.20
none
none
Water
phase
0.04
none
none
none
none
none
1.15
Total
100.46
100.04
105.05
80.63
115.20
100.40
99.40
119
0.19
l -
O N ( ? . - N
99999
0 0 0 0 0
0.01 9
Ni
hl9999
0 0 0 0 0
--
o q m ~ c n
83.37
0.4
0.02
14.63
16.12
14.72
14.70
17.19
15.47
98.0
67.00
66.17
67.35
66.20
66.75
66.69
Average
cn
0,
Extracted,
per cent
-00,
periment
number
>99.9
none
Pt
2
cn
so ic
P C
4-
x i
LLIC
* Ru and lr are not extracted in the concentrate

** the concentrate additionallv contains - 1% SO:
looI2O.O
0.54
0.009
82.48
82.84
02.73
84.71
84.13
0.007
0.009
0.01 0
0.012
0.008
9.61
9.90
10.10
9.73
8.95
Total
precious
metals
Se
Te
cn
!3
s
0.009
0.020
0.037
0.018
0.024
Fe
c n o r - m e
Pd
--
0.22
0.15
0.18
0.32
0.26
0.22
0 0 0 0 0
.
Y
I
NCDcDrncn
LI
.
I
0.12
0.16
0.26
0.23
0.19
cu
Rh
The Composition of Noble Metals Concentrates Obtained from Copper-Nickel Anode Mud Solutions
by the Hydrocarbonylation Process, per cent, per cent
Table II
Total
non-ferrous
metals
usual rules that are obeyed by

other binary systems, for example: palladium(I1)-copper (11),
palladium(I1)-iron(III),platin~ r n - C O P P e r r npalla&=rn,
platinum(IV) and other similar
binary aqueous systems:
(a) before palladium and platinum are precipitated, copper(I1) and iron(II1) are catalytically reduced to copper(1)
and iron(I1)
(b) before platinum is precipitated, platinum(IV) is reduced
(also catalytically) to platinum(I1)
(c) rhodium(III),
ruthenium(1V) and iridium(IV) are
reduced to the lower carbonylchloride
complexes:
[Rh(CO)2C12]-,
[Ru(CO)~CL]'.,respectively,
and [Ir(C0)2C12]
which are easily extracted by
various organic reagents, for
example, butyl phosphate.
The metals which are
extracted from processing the
copper anode mud solution are
listed in Table I. Carbon
monoxide was added at atmospheric pressure to the initial
solution which was held at a
temperature of about 100C for
four hours.
The precipitation of rhodium
from its various chlorocomplex
solutions depends mainly on the
temperature and the concentration of the hydrochloric acid.
However, the presence of other
platinum metals in the solution
considerably affects the precipitation of the rhodium.
Therefore, we can arrive at a situation where rhodium practically does not precipitate in the
first concentrate, concentrateI, if the hydrocarbonylation
120
process is carried out at a temperature of 60C

or less, and the concentration of the hydrochloric acid is greater than 1 molllitre.
Besides platinum, palladium, gold and silver, the metals selenium and tellurium are also
precipitated out in concentrate-I. However,
Table I shows the composition of concentrateI after it has been heated to 9OO"C, which is why
the selenium and tellurium are missing.
In order to obtain concentrate-I, from which
the metals rhodium, ruthenium and iridium can
be extracted, and to study the behaviour of selenium and tellurium during this process, we carried out a series of experimentsusing the hydrocarbonylation process on a solution of nickel
anode muds.
The composition of the nickel anode muds,
in gramdlitre, was as follows: copper 15.52;
nickel 10.47; iron 3.03; sulphate, SO:., 16.4;
chloride, C1-, 212.3; and in milligramsllitre the
following: selenium 170.6; tellurium 101.8; palladium 1134.0; platinum 321.4; rhodium 41.4;
ruthenium 8.67; iridium 3.58; gold 0.17 and silver 86.7. Carbon monoxide was passed through
the initial solution, which was held at a temperature below 60C, and thoroughly mixed for
3 to 4 hours. A black powder (concentrate-I)
was obtained. It precipitated easily and was simple to filter. The composition of the obtained
concentrates and the proportions of the extracted
metals are shown in Table 11.
The results of the experiments confirm that
by the reaction of carbon monoxide with solutions of copper and nickel anode muds, a high
quality platinum-palladium concentrate can be
obtained with:
a high selectivity to the platinum group
metals and only small admixture of non-ferrous
metals (0.2 to 0.3 per cent)
a high noble metal concentration (82 to 84
per cent)
Besides the high quality of concentrate-I, it
is also possible to achieve a high yield of platinum, palladium, gold, selenium and tellurium
in the concentrate.
The process of hydrocarbonylation can be used
for selective precipitation of metals from more
concentrated solutions. For example, we have
used a solution with the following composition,

in gramshtre: platinum 18.4; palladium 5 1.O;
rhodium 6.5; iridium 2.9; gold 1.02; copper
16.2; nickel 3.8; iron 1.90; selenium 2.6; tellurium 3.2 and hydrochloric acid 110. Because
of the carbon dioxide, selenium, tellurium, gold
and palladium are precipitated; platinum is precipitated at 96 to 98 per cent, but the total
amount of rhodium and iridium precipitated
is less than 5 per cent. These results therefore
confirm the practicality of obtaining platinum
group metals concentrates from complex solutions, using the hydrocarbonylation process.
Regeneration of the Platinum

Metals from their Alloys
A considerable quantity of the platinum group
metals are in circulation at any one time, and
recycling them from their various alloys presents
an important technologicalproblem. It has been
reported that carbon monoxide can be used to
separate rhodium or iridium from the other platinum group metals (3). However, the processes
which achieved this were performed in dilute
acids, but dissolving the alloys in the hydrochloric acid + chlorine gas system produces solutions containinghighly concentrated hydrochloric acid. These must be neutralised by the
addition of sodium hydroxide, thus this process
produces waste.
We have been investigating the possibility of
recovering the platinum metals from solutions
containing a high concentration of hydrochloric acid, for systems of the chlorocomplexes of
palladium(I1)-platinum(IV), platinum(1V)rhodium(II1) and platinum(1V)-iridium(1V).
Palladium, platinum and rhodium can be
obtained as metallic powders by the action of
carbon monoxide on solutions of the single
chlorocomplexes in hydrochloric acid. The rate
of the reductions is:
palladium(I1) > platinum(IV) > rhodium(II1).
This process has an induction period, T k d , the

duration of which is a function of the type of
metal, the temperature and the concentrations
of chlorine and hydrogen ions.
Therefore, there is every reason to think that
121
Table 111
Results of the HydrocarbonylationProcess in the H2PtC16-H&hC16-HCISystem

Experimental
conditions
Composition of the solutions
Pt'", gll
Precipitation of
metals, per cent
Rh"', gll
HC1, M
Temperature, O C
Time, h
Pt
Rh
30.8
12.3
4.4
4.4
6
3
4
4
75
50
50
25
4
4
5
6
77.5
99.2
99.5
99.7
3.3
2.3
0.9
0.1
40.5
29.2
30.2
30.2
I
I
Table IV
Results of the HydrocarbonylationProcess in the

Platinum(1V)-Iridium(1V)-HCI System
Pt'",gll
I?. gll
HCI, M
Temperature, O C
Time, h
Pt
23.2
8.5
8.5
6
0.6
1 .o
75
75
75
2.5
2.5
2.5
99.90
99.99
99.99
28.0
41 .O*
41 .O"
* the mixture (NH&PtCI,
Precipitation of
metals, per cent
Experimental
conditions
Ir
0.08
0.24
0.10
(NH4)212CIt
was used here
Table V
Effects of the HydrocarbonylationProcess in the H2PtCl6-H~dCl4-HCI

System
___________~
Pt'", g/l
33.2
53.2
45.0
45.0
45.0
45.0
7.2
45.0
2.0
Pd", g/l
HCI, M
30.8
30.8
15.8
15.8
15.8
15.8
7.5
15.8
2.0
6
6
6
8
6
6
4
6
3
Temperature, O C
25
25
40
40
50
50
60
70
75
these metals can be separated by modifying the

composition of the solution and by adjusting
the temperature. Thus, carbon monoxide was
bubbled through the initial solutions at atmospheric pressure, while undergoing a thorough
Experimental
conditions
~
Time, h
.o
1
1.5
1.5
2.0
4.0
2.0
0.5
2.5
1
.o
Precipitation of
metals, per cent
Pd
Pt
83.20
99.98
96.70
99.40
93.70
99.99
79.90
99.70
99.8
3.2
6.3
2.1
3.4
2.0
3.7
7.6
8.4
10.1
mixing at a temperature of 25 to 75C.

The composition of the solutions and the
experimental data are shown in Tables I11 to V.
Our assumption was confirmed for the systems
platinum(1V)-rhodium(II1) and platinum(IV)-
122
Table VI
The Effects of the Preparation Conditions on the Characteristics

of the Palladium Powders
Sample
Sample
2
3
4
Experimental conditions
Specific
surface,
Volume
density,
PdW. gll
HCI, M
Temperature, OC
m2/g
g/cm3
44.0
50.0
55.0
76.0
46.0
35
80
80
80
80
9.1
4.2
3.1
1.7
0.74
0.91
1.34
1.89
2.1 1
2.60
1
1
1
6
By using the concentrations of palladium and

hydrochloric acid, and the temperature as the
variables, we have obtained the equation of the
regression, which correlates these parameters
with the value of the volume density of the palladium powders. Experimental results are shown
in Table VI.
Analysis of the experimental data has enabled
us to produce palladium powders with the necessary physicochemical properties for use in
electronics, according to the following rules:
for powders with low volume density and
small particle size, the hydrocarbonylation
Preparation of Palladium and
process should be performed at room temperPlatinum Powders
Metallic powders of palladium, platinum and ature in low concentrationsof hydrochloric acid;
to obtain powders with greater volume dentheir alloys find wide application in the electronics industry. They are obtained by the reduc- sity and larger particle size, the hydrocarbonytion of corresponding solutions using, for exam- lation should be carried out at about 80C in
high concentrations of hydrochloric acid.
ple, hydrazine.
For electronic applications palladium powders
We have studied the possibility of utilising the
hydrocarbonylation process for obtaining plat- must be thermally stable. To test for this, saminum metals powders with the required physico- ples of palladium powders were investigated by
chemical properties for these uses, such as speci- thermography. The samples were distributed
fic surface area, volume density, dispersion and into two groups:
(i) thermally stable powders having oxidation
resistance to oxidation.
For palladium, the rate of reduction in the temperatures higher than 500C with the proPd(II)-H'-CT-H20-C0 system can be expressed portion of oxidised palladium being around
20 to 30 per cent
in the following way (7):
(ii) thermally unstable powders having oxidCpd/dT = K . C d . C-'H+. C-'cr. C'H,O . Cco
dation temperatures of 200 to 280C with the
where C represents the concentration of each proportion of oxidised palladium being above
component in the system and K is the reaction 70 per cent.
From all the experimental data, we have
constant for this particular reduction, z is time.
iridium(1V): in both cases platinum can be

almost completely precipitated with only a little admixture of the other platinum metal.
However, a different reaction occurred in the
platinum(W)-palladium(II) system where up to
about 10 weight per cent of platinum, together
with palladium, is precipitated over a wide range
of temperatures and hydrochloric acid concentrations, see Table V. This is probably due to
the formation of rather stable heteronuclear carbony1 complexes of palladium-platinum.
123
Table VII
ThermomechanicalData of Platinum Wire

1 m m in Diameter Containing + 0.25 weight per cent Zirconia
Sample
a,MPa
2OoC
I*
2""
0,per
llOOC
350
293
60
60
2OoC
8
14
Temperature, 11OOOC
cent
llOOC
8
4
Loading,
MPa
Timeto
gap, min
percent
50 --3 45
40
7
32
17
7.5
E.
0 02
58.5
56
'The wire was first annealed in hydrogen at 95OoC for 30 minutes

* * The wire was first annealed in vacuum at 1 100C for 20 minutes
a the stretch of the sample at the moment of destruction (in per cent)
strength (limit)
E
relative strain
0 0 2
conventional tensile yield limit
"Time to gap" is the time needed for the destruction of the sample
I&
der of platinum and 0.25 weight per cent

zirconium oxide was obtained by hydrocarbonylation from initial solutions containing platinum(IV) and zirconium oxide. From this powAlloy Powders
der, a resulting compact metal was produced,
Using the hydrocarbonylation process for the having a hardness of 137.2 to 142.6 W.The
production of platinum and palladium alloy pow- results of thermomechanical tests are given in
ders has also been examined. A solution of H2PtCI, Table VII.
and H2PdC14was reacted with carbon monoxide under atmospheric pressure at a tempera- Preparation of Supported Catalysts
ture of around 80C for three to five hours. Phase
Redox decomposition of the carbonylchloride
analysis showed that the alloy powders obtained complexes of palladium(I), platinum(1) and
were solid solutionswith a concentration of chlo- rhodium(1) was used for the preparation of suprine ions less than 0.005 weight per cent (8).
ported catalysts. A catalyst containing 3 weight
per cent palladium supported on alumina was
Dispersion Strengthened Material
prepared by the decomposition of water-organic
The hydrocarbonylation process may also be solutions of the palladium(1) carbonylchloride
used for obtaining dispersion strengthened mate- complex on alumina. This palladiudalumina
rials, such as platinum-zirconium oxide. A pow- material was then tested as a hydrogenation
concluded that palladium powders, suitable for

use in electronic applications, can be produced
by the hydrocarbonylation process.
Table Vlll
Test Results of Palladium and Platinum Catalysts for the Reduction of

Propylene into Glycols
Sample
1
2
3
4
5
support
Ti02
charcoal
Catalyst composition*,
mol
Relative
activity
Selectivity,
per cent
Pd : Pt = 7.8 : 1
Pd : Pt = 6.5 : 1
Pd : Pt = 6.0 : 1
96
116
128
75
80
85
Pd : Pt = 6.0 : 1
Pd : Pt = 7.5 : 1
66
74
78
76
* A l l samples contained 3 weight per cent of the metals

Relative activity is the catalyst activity with regard to some standard sample
Platinum Metals Rev., 1996,40,(3)
124
catalyst for phenylacetylene. It had high activity and produced more than 10 litres of HJmidg
Pd with 94.5 per cent selectivity (9). This is better than results from the same catalyst which
has been produced by other methods.
Catalysts with supports such as titania and
charcoal, were obtained using the same method
from binary solutions of the carbonylchloride
complexes of the platinum metals (platinum and
palladium). Results of tests using them are
shown in Table VIII. These catalysts have the
same activity and selectivity as catalysts prepared by standard methods, however, their
method of production is simpler.
Conclusions
Thus, the results of our investigations show
that the hydrocarbonylation process and carbony1 complexes of the platinum matals can
be used for the concentration, extraction and

refining of the platinum group metals. The use
of these processes for the production of composite materials and processing by powder metallurgical methods offers a potentially successful alternative to current means of production.
However, as yet, these methods have not been
put to industrial use.
References
Platinum Metals Rev., 1991, 35, (2),96
French Patent 2,305,398; 1976
British Patent 1,472,176;1977
British Patent 1,507,792;1978
US.Patenr4,163,664;1979
Russian Patent 1,637,352; 1990
V. I. Spi-,
I. V. Fedoseyev and I. V.Znamensky,
J. Inorg. Chem., 1980,25, (lo), 2754
8 Russian Patent 1,541,894; 1989
9 Russian Patent 1,593,008; 1990
1
2
3
4
5
6
7
Single Platinum-Rhodium Gauze for Partial Oxidation

TheFossibilityof using a small reactor for converting the light alkanes found in remote natural gases into more useful liquid fuels and commercial products, by an efficient and fast process,
has been suggested in work performed by scientists at the University of Minnesota (D. A.
Goetsch and L. D. Schmidt, Microsecond
Catalytic Partial Oxidation of Alkanes, Science,
1996, 271, (5255), 1560-1562).
Using a single layer of woven platinum-10 percent rhodium gauze, they were able to perform
catalytic reactions of microsecond duration at
atmospheric pressures with very high reaction
rates. This allowed selective partial oxidation of
the reactants to take place. Reacting gases were
heated from room temperature to > 800 C, on
entering the single layer of gauze, for a contact
time of 8 to 500 ps. After reaction the products
were rapidly quenched from 800C to 400C
within 200 ps, as they mixed with the cold
unreacted gases that had passed between the
gauze wires of the catalyst. This allows selective
production and survival of oxygenates.
A single Pt gauze catalyst layer produces high
oxygen conversions and very different selectivities from coated monoliths or multiple gauzes,
with parent olefin, formaldehyde and acetaldehyde being the most partially oxidated products. For ethane, propane, n-butane and isobutane different reactivities and selectivities were
observed selectivity to olehs strongly decreased,
while selectivity to oxygenates increased with
Platinum Metals R m . , 1996, 40, ( 3 )
alkyl chain length. At least 40% of reacted

butane was converted, mostly to formaldehyde
and acetaldehyde.
Steady conversions and selectivities were
reached after several hours, with temperatures
at > 800C. The near-adiabatic conditions prevent carbon formation.
Besides being used as a single gauze, the gauze
may also be used to preheat gases for partial oxiThese
dation by oxide catalysts, such as VzOs.
catalysts produce partially oxidised products
with high selectivity and require very high ignition temperatures, so preheating is necessary
for high conversions and adiabatic operation. A
single platinum gauze, placed in front of the
oxide catalyst, could preheat the gases to the
required temperature. Rapid quenching would
keep the conversion low so alkanes and oxygen would remain for reaction on the catalyst.
The reactor has also been operated at 70 d s ,
which suggests that sonic flow could be obtained,
with supersonic quenching. This increased speed
of reaction might further stabilise useful chemical species.
At present, the reactors are producing 20
kg/day of aldehydes and butylene from butane.
A reactor of 0.3 m diameter could produce
1000 metric tondday at 70 d s under these conditions. With higher pressures and velocities,
and ifproducts are removed and reactants added
between catalyst layers, even higher yields and
greater selectivities may result.
125
Palladium Catalysts in Organic Synthesis

Palladium Reagents and Catalysts - Innovations in Organic Synthesis
BY JIRO TSW, John Wiley & Sons, Chichester, 1995, 574 pages, ISBN 0471-95483-7, E125.00
The main catalysts which are traditionally used

for the hydrogenation of organic compounds
are supported platinum group metals, and while
these heterogeneous catalysts are generally not
effective in carbon-carbon bond forming reactions, there has been a growing interest in recent
years in soluble complexes of the platinum group
metals for use as catalysts in organic synthesis.
Rhodium catalysed alkene hydroformylation
and carbonylation of methanol to acetic acid are
two particularly notable industrial successes
in this area, and there have also been many
dramatic advances in laboratory-scale carboncarbon bond forming reactions.
A tremendous amount of research has shown
that palladium is one of the most versatile centres in this context, and many otherwise difficult-to-achieve organic transformations can
be accomplished in convenient practical procedures, when mediated by soluble palladium
species. This is illustrated by two important reaction types: coupling processes - of the kinds
developed by R. F. Heck and reviewed in his
book Palladium Reagents in Organic
Synthesis, Academic Press, 1985; and direct
incorporation of carbon monoxide into certain organic compounds to give a variety of carbony1 derivatives (aldehydes, carboxylic acids,
amides, esters, etc.) - often under conditions as
mild as room temperature and atmospheric pressure, which palladium compounds have the ability to promote. A book on these reactions by the
present reviewer and his colleagues appeared
more recently (Carbonylation - Direct
Synthesis of Carbonyl Compounds, by H. M.
Colquhoun, D. J. Thompson and M. V. Twigg,
Plenum Press, 199 1 (1)).
The present book is to be welcomed, since it
not only gives an update of progress in the two
areas mentioned, but also embraces the entire
field of palladium reagents and catalysts in
organic synthesis. I n his authoritative book
Professor Tsuji provides more than 2400 orig-
Platinum Metals Rev., 1996, 40, (3), 126-127
inal literature references, as well as information

about relevant monographs and other texts. It
comprises three short and two long chapters.
The first chapter, of only ten pages, describes
characteristic features of palladium catalysed
reactions, and fundamental concepts in palladium organometallic chemistry. The second,
even shorter, chapter (six pages) describes how
reactions are classified in the book, while the
third chapter, of over one hundred pages, deals
with oxidation reactions involving palladium(II),
such as Wacker chemistry (alkenes to aldehydes, etc.). The fourth chapter is very long, some
four hundred pages, and is concerned with carbon-carbon bond forming reactions. The fifth
and final chapter, of twenty pages, brings
together various catalysed reactions, which have
unclear mechanisms, or which, for other reasons, do not fit into any of the categories of
the two main chapters.
The index is useful, although not exhaustive.
References are collected at the end of chapters
and also at the end of some main sections in the
largest chapter; this could cause confusion for
readers wishing to pursue the original papers.
The two other previously mentioned books give
practical details for those wanting to make use
of palladium-based procedures in their own
work. In contrast, the present book does not
provide such information, but as the discussion
is detailed, and there are copious references,
there should be no major problems translating
theory into practical applications.
As suggested by the layout of the chapters,
material is organised according to the involvement of the metal, while in the two main chapters it is organised according to the organic transformations. This could make it rather difficult
for a reader who wants to establish how palladium catalysis might help with a particular transformation. However, by using the contents list
and the index, specific information can be
tracked down. Due to the wealth of informa-
126
tion it contains, browsing through this book will

always be a rewarding experience. It is nicely
produced, and is an important addition to books
about modern applications of palladium chemistry to organic synthesis. It is comprehensive
in the literature coverage to early 1994, and it
is recommended for purchase by research

libraries associated with palladium chemistry or
synthetic organic chemistry.
M.V.T.
Reference
1 Plurinum Metals Rev., 1992,36, (l), 39
Platinum Complexes Used in DNA Binding Studies

DNA binding studies need unsaturated complexes with emissions sensitive to environmental
changes to bind to DNA. Some ruthenium and
platinum complexes have photoluminescence
changes upon intercalation into calf-thymus (ct)
DNA. Scientists at the University of Hong Kong,
(H.-Q.
Liu,T.-C. Cheung and C.-M. Che, Chem.
Cummun., 1996, (9), 1039-1040) have now found
two platinum complexes with dramatically en-
hanced photoluminescence on binding. [ptn(dppC,N,N)(MeCN)] had a 271-fold increase in

emission and [Pt2(pby-C,N,N)2(p-dppm)]2+
had a 117-fold increase; dpp-C,N,iV = C-deprotonated 2,9-diphenyl-l,lO-phenanthroline;pbyC,N,N = C-deprotonated 6-phenyl-2,2-bipyridine and dppm = diphenylphosphinomethane.
This is attributed to intercalation into ct DNA,
and may be used as luminescent switches for DNA.
Platinum 1996
For more than a decade Johnson Matthey
has conducted an annual survey of commercial aspects of the platinum metals, and
presented the findings in a comprehensive
yet readable fifty-two page review.
The recently launched Platinum 1996
records that during 1995 a recovery in
South African production and increased
Russian shipments lifted platinum supplies
by 10 per cent to 4.98 million oz, while
platinum demand improved by 5 per cent
to a new peak of 4.79 million oz. Despite
a fall of 20,000 oz, at 1.85 million oz autocatalyst manufacture still formed the
major requirement for platinum, followed
by jewellery with an increased demand of
1.81 million oz.
It is interesting to note that usage by the
automotive industry is not confined to
emission control catalyst manufacture.
Platinum-tipped spark plugs continue to
replace base metal plugs on new vehicles,
the oxygen sensors used in engine management systems employ platinum, and the
lightweight plastics increasingly used in
body parts and engine components are reinforced with glass fibre formed using platinum bushings. In addition, the petroleum
industry uses platinum catalysts in the
production of gasoline and cleaner-burning diesel fuels, while for the future, proton exchange membrane fuel cells could
be used to power zero emission vehicles.

During 1995 industrial demand for platinum increased by 2 1 per cent to 990,000
02, the highest level for sixteen years. At
the same time sales of palladium for electronics applications rose by 19 per cent to
2.65 million oz, while high demand from
the chemical and glass industries boosted
industrial off-take for rhodium by 12 per
cent to 48,000 oz. Despite a 12 per cent
increase in demand for ruthenium from the
electronics industry, a decline in purchases
by electrochemicalcompanies contributed
to an overall fall in demand of almost 5 per
cent, compared with 1994. Iridium demand
increased from 42,000 oz in 1994 to 52,000
oz in 1995; although the electrochemical
sector accounts for about half of the
demand for iridium, smaller applications
including crucibles, biomedical and spark
plug tips for aerospace applications all
increased.
Readers of Platinum Metals Review who
wish to have access to this authoratitive
source of information on the many factors that influence the supply and demand
of the platinum metals are invited to direct
their request for a free copy of Platinum
1996 to the author: Alison Cowley,
Johnson Matthey PLC, 78 Hatton Garden,
London EClN8JP, England; Fax: +44171-269-8389.
127
Ruthenium: A Dance to the

Music of Time
By Professor K. R. Seddon
School of Chemistry, The Queens University of Belfast
This short review was written to celebrate simultaneously the one hundred
andfijlieth anniversary of the discovery of ruthenium by K . K . Klaus, and
the bicentenary of his birth. A personal and (necessarily) selective overview o j
the highlights of the past decade of ruthenium chemistry is presented, and an
attempt is made to place these in an historical perspective.
The year 1994 marked the one hundred and
fiftieth anniversary of the isolation of ruthenium
by Karl Karlovitch Klaus (1796-1864). K. K.
Klaus (Carl Ernst Claus is the Germanic form
of his name) was born and died in Dorpat (now
Tartu, in Estonia), and 1996 is the bicentenary
of his birth. A number of excellent accounts
of his life and scientific work already exist (1,
2), and an article, soon to be published here,
will carry a new perspective of his work (3). The
purpose of this review, therefore, is to mark these
anniversaries by selecting some of the advances
in ruthenium chemistry over the last ten years,
and placing them in an historical perspective.
They are waiting on the shingle

They are waiting on the shingle - will you
come and join the dance?
Will you, wont you, will you, wont you, will
you join the dance?
Will you, wont you, will you, wont you,
wont you join the dance?
Lewis Carroll, Alices Adventures in Wonderland
Between 1951 and 1975, Anthony Powell published a sequence of twelve related novels under
the title A Dance to the Music of Time(4),
fkom the Poussin painting, Figure 1. These novels, which can only be read as a whole, represent a unique view of British twentieth century life. The characters pursue an intricate
temporal Terpsichorean path, with characters
of initial colossal importance disappearing, while
others, some of whom dominate the sequence,
appear initially insignificant. The novels rep-
Platinum Metals Rev., 1996,40, (3), 128-134
resent the personal impressions of a narrator of

selective events and their complex temporal
interrelation. In his view the characters perform
a dance to the music of time, reminiscent of
Poussins scene, in which the Seasons, hand
in hand, facing outward, tread in rhythm to
the notes of the lyre that the winged and naked
greybeard plays.
T h e chemistry of ruthenium also seems to

be dominated by this mythical being; some compounds reported in the original accounts of the
discovery of ruthenium ( 5 ) still are of prime
importance today, others attract only passing
interest. Some of the developments reported in
the following pages were unimaginable in 1844,
others are a natural consequence of the observations made by Klaus. Some complexes, such
as [R~(bipy),]~
(bipy = 2,2-bipyridine), appear
as mildly interesting upon their discovery in
1936 (6), but blossom into supreme importance
much later, in 1976 (7).
Where shall I begin?

Where shall I begin, please your Majesty?
he asked. Begin at the beginning, the King
said, very gravely, and go on till you come to
the end: then stop.
Lewis Carroll, Alices Adventures in Wonderland
Georges Franju: Movies should have a
beginning, a middle and an end.
Jean-Luc Goddard: Certainly. But not
necessarily in that order
Time, 14th September, 1981
So, whose advice to follow? 111 opt for Powell
128
Fig. 1 LL Dance to the

Music of Time, by N.
Poussin, 1594-1665;
(reproduced with permission from the
Wallace Collection)
and Goddard, ignore Carroll, and begin in 1984,

when I co-authored a monograph entitled The
Chemistry of Ruthenium ( 8 ) . This was supplemented by a series of annual reviews in
Coordination Chemistry Reviews (9-16). Later,
the text was complemented by the appearance
of articles in Comprehensive Coordination
Chemistry (1 7), Comprehensive Organometallic Chemistry (18-26),and entries in the
Dictionary of Inorganic Compounds (27-29).
If this wealth of published review material is
combined with the now routine and cheap online access to Chemical Abstracts and Science
Citation Index, it will be appreciated that a short
review of the chemistry of ruthenium, even
restricted to the past decade, will add little of
value to the literature, as it cannot hope to be
either comprehensiveor even cover all the major
highlights.
The magnitude of the problem will be seen by
examining the trend in published papers concerning the chemistry of ruthenium, see Figure
2.In 1967, Griffith published an essentially
comprehensive review of the chemistry of ruthenium, from its discovery up to 1966 (30): the
coverage included 408 citations. In 1984, my
book appeared, giving comprehensivecoverage
of the ruthenium literature from 1804 to 1978
(8): it cited 3254 references. Between 1981 and

1995, Science Citation Index (via the Bath
Information and Data Services) lists 1 1,100 references citing ruthenium: there were 1407
papers in 1995 alone (more than three times the
total number published from 1844 to 1966).
The annual review of only the co-ordination
chemistry of ruthenium (no organometallic compounds included) for 1993 lists 405 references
(1 6).The literature concerning, and interest in,
ruthenium is burgeoning. If this rate of publication continues (and with increasing pressures
to publish in academia, it will), we should anticipate over 25,000 papers by the year 2005. It
16000
ul
U
L 12000
k
h.
8000
4000
f2
1966
1978
1995
YEAR
Fig. 2 The trend in the integrated appearance

of papers about ruthenium chemistry up to
1995
129
4-
CI
CI
CI
Fig. 3 The dodecachlorotrirutheuate (4 -) ion: a clue to

the structure of ruthenium blue
CI
should be remembered, however, that there is

no established link between quantity and quality; it is also evident that ruthenium is no longer
considered to be an expensive metal! (The average Johnson Matthey base price for ruthenium
for May 1996 was $1.77/g). It would not be a
daring prediction to suggest that the percentage of handle-turning pot-boilers will be increasing at a rate proportional to the publication rate.
So, where do I begin? Let us this time listen to
Lewis Carroll.
The beginning
'The characters of this metal [ruthenium] are so
distinct, that no doubt can be entertained as to its
being Werent fkom all previously b o r n . Its highest chloride has a fine orange colour; and when
ammonia is added to its aqueous solution, a black
oxide is precipitated, whereas the solutions of
the other platina metals are not precipitated at
all by ammonia at common temperatures. The
solution of the chloride is not altered by hydrosulphuric acid (H'S) till the action has been long
continued, and then a brown precipitate is at first
obtained, which afterwards becomes a black sulphuret, and the solution assumes a magnificent
azure-blue colour. These changes depend upon
the precipitation of a small portion of metallic sulphuret and the conversion of the chloride into a
higher one, which has a blue colour, and which
is not decomposed by the hydrosulphuric acid.
If a plate of zinc be put into the solution of the
orange chloride, acidified by a little hydrochloric

acid, a black metallic powder is precipitated after
some time, and the solution becomes of a deep
indigo-blue colour; eventually the whole of the
metal is precipitated, and the solution becomes
colourless.'
C. Claus, 1845 ( 5 )
One of the abiding mysteries of ruthenium

chemistry is the nature of ruthenium blue
(ascribed to ruthenium for the first time, in
English, in the above quote). Forty years before
Klaus discovered ruthenium, Fourcroy and
Vauquelin noted that the action of zinc upon
certain solutions of the platinum metals generated an azure-blue solution (31-33). Ten years
later, Vauquelin attributed this blue colour to
iridium (34,35). In 1846, Claus demonstrated
that this blue colour was characteristic of ruthenium chemistry, suggesting that it was due to
the presence of RuCL in solution (36).
In 1996, we are little further forward in identifying the complex responsible for this colour,
despite the extensive use of ruthenium blue as
a synthetic reagent (8). The closest clue to the
identity of ruthenium blue is a mixed-valence
salt isolated by Bin0 and Cotton (37), containing the [Ru3CllrI4anion, see Figure 3.
Recently, see Figure 4, mixed-valence phosphine derivatives of this anion, [ R U ~ C ~ ~ ( P R ~ ) ~ ] +
Fig. 4 Mixed-valencephosphine
derivatives of the ion shown in
Figure 3, [RusCI.(PR3)r]', R =
Et or Bu
130
(where R = Et or Bu) have also been isolated,

and characterised (3840).
13The past ten years have also seen many simple halide complexes redefined, or observed in
a pure form for the first time.
The anion [RU~OB~,~],
analogous to the well
established [RuzOCllo]~
(1 l), has been shown
Br
0r
Br
not to exist (41); salts of this anion which have
been reported in the literature (42, 43) were
Fig. 5 The anion [Ru,Brr]- has an almost
idealised confacial bioctahedral structure,
demonstrated to be salts of [RuzBr9Is,an anion
containing a metal-metal interaction
with an almost idealised confacial bioctahedral structure, see Figure 5, but containing a
significant metal-metal interaction { r(Ru-Ru)
= 0.2880 nm}.
to Klaus, in the first report of the discovery of
The hexachlororuthenate(II1) anion has been ruthenium. Connoisseurs of ruthenium chemgenerated in solution in ambient-temperature istry will recognise the blackish-green mass
chloroaluminate(II1) ionic liquids by electro- described above as potassium ruthenate(V1) ,
chemical reduction of hexachlororuthenate(IV) Kz[Ru04].Hz0(52), which dissolves in water
(44), and the electrochemistry of the [ R U C ~ ~ ] to~ give an orange solution.
couple has also been recently investigated in
The barium analogue of this salt was reported
conventional molecular solvents (45).
in 1888 (53), however, it was almost one hunTwelve years ago, an important paper appeared dred years before it was recognised that the bar(46)describing the formation of the novel salts ium salt contained not the expected tetrahedral
A[RuO,CL] (A = [PPh,] or [AsPh,]), which now (Td)tetraoxoruthenate(VI) anion, but the fivehave a widespread utility as organic oxidants co-ordinate trigonal bipyramidal (D3h)dihy(converting alcohols to aldehydes and ketones, droxytrioxoruthenate(V1) species, see Figure
without attacking C=C double bonds) (47-50).
6 (54).
The green anion in these salts was tentatively
Klaus noted that potassium ruthenate(VI)
described as a dimeric species, [Ru,O,Clr], in
blackens organic bodies, and is decomposed by
the solid state, but as a monomer, [Ru02Cls]-,
the addition of organic substances, such as alcoin solution (46). It is now known to be fivehol, and also by the action of acids, &c. (5).
co-ordinate in both solution and the solid-state,
although its precise geometry is cation depenThis astute observation predates by nearly 150
years the use of rutheniumw) as an important
dant (51).
oxidising agent in organic chemistry, chemistry
The metal [ruthenium] thus obtained, and all its

combinations, when mixed with a large quantity
of nitre and heated strongly to redness, give a blackish-green mass, which, when dissolved in water,
yields a solution of a fine orange-red colour. This
solutionof the potash salt of the metaUic acid blackens organic bodies, and is decomposedby the addition of organic substances, such as alcohol, and
also by the action of acids, &c.; and there is precipitated a velvet-black compound of the oxide
and potash; this is soluble in boiling hydrochloric acid, and yields an orange-coloured solution
of the chloride.
C. Claus, 1845 (5)
Continuing on our intricate temporal Terpsichorean path, the above quote returns us again
Fig. 6 The five-co-ordinate bipyramidal

dihydroxytriororuthenate(V1) species
131
that has been dominated by the excellent work

of Griffith (46,47,49, 55, 56), although other
scientists have been active too (57, 58).
Will you come and join the dance?

Of course, some of the most interesting chemistry which has appeared in the last decade was
not even suspected in the nineteenth century.
Some (but by no means all) of the most notable
examples of exciting new chemistry have
included:
The reaction between [Ru(CO)~]and buckminsterfullerene, C,,, in toluene produces the
complex [RU(CO)~(~-C~O)]
(59).
Molecular wires with directional photoinduced electron transfer, based on alkynesubstituted terpyridine ligands, such as (terpyCa-terpy, see Figure 7), have been developed
(60-63): complexes include such species as
[ (terpy)Ru(pterpy-Ca-terpy)M(p-terpy-Caterpy) Ru(terpy)],. (M = Fe, Co or Zn; terpy
= 2,2:6,2-terpyridine).
A perfluorinated ruthenium(I1) phthalocyanine complex, [Ru(F,,Pc)] has been encapsulated in zeolite NaX, and used (in the presence of tert-butyl hydroperoxide) to oxidise
cyclohexane at room temperature (64-66),
whereas a simple water-soluble ruthenium(I1)
phthalocyanine complex, K[Ru(Pc)L2] (LH =
diphenylbhenyl-3-sulfonic acid)phosphine ,see
Figure 8) is an exceptionally active agent for
photodynamic cancer therapy (67).
[Ru(CO),]* has been prepared for the first
Fig. 7 The ligand terpy-C*-terpy,which has

been used in the development of molecular
wires, based on ruthenium complexes
Fig. 8 The water-soluble ruthenium complex

K[Ru(Pc)L2] is an exceptionally active agent
for photodynamic cancer therapy, where LH
represents diphenyl(pheny1-3-sulfonic acid)
phosphiue
time, as a thermally-stable [Sb2FII]salt, by

the reductive carbonylation of Ru(SO,F), under
one atmosphere of carbon monoxide at 60 to
90C (68).
Sr2Ru0,has been shown to be a copper-free
superconductor (69, 70).
Gratzel has developed an efficient nanocrystalline photovoltaic device, using cis-di(thiocyanato)bis(2,2-bipyridine-4,4-dicarboxylato)
ruthenate(I1) as the sensitiser (71).
In perhaps one of the most elegant synthetic
studies in ruthenium chemistry of this century,
Newkome and his co-workers have prepared
ruthenium-containing dendrimers, as illustrated
in Figure 9, containing twelve ruthenium atoms
(72-74). The isolated salts are red, crystalline
materials.
Come to the end: then stop

As is evident from the flavour of the papers
discussed above, ruthenium continues to deliver
some of the most exciting chemistry to be found
today. Perhaps this is not surprising in the element which exhibits the most oxidation states
in the Periodic Table. The number of papers
published is growing at a phenomenal rate, as
is the amount of tedious trivia, but the quality
of the best work is quite outstanding. No chemist
could read the highlights of the past few years,
presented here, without feeling a thrill of excitement, a debt of gratitude to Klaus, and without
wanting to join the dance. And so:
On with the dance! let joy be unconfind
Lord Byron, Childe Harold, 1812-1817.
132
Fig. 9 A metallomicallauol (R = CH2CHs), containing twelve ruthenium atoms
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A Buyers Market, 1952; The Acceptance
World, 1953; At Lady Mollys, 1957;
Casanovas Chinese Restaurant, 1960; The
Kindly Ones, 1962; The Valley of Bones, 1964;
The Soldiers Art, 1966; The Military
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134
ABSTRACTS
of current literature on the platinum metals and their alloys
PROPERTIES
High Coercivity in ColPt Multilayers
Jpn.3 Appl. Phys., 1996, 35,
(lB),342-345
Magnetic Excitations and the Search for

Crystal-Field Transitions in the HeavyFermion SuperconductorWd2Al,
J.-H. KIM and s.-c.SHIN,
A. KRIMMEL, A. LOIDL, R ECCLESTON, c. GEIBEL and F.

STEGLICH,
Phys..: Condens. Mutter, 1996, 8, (1 l),
The coercivity in a CoPt multilayer on a Si& underlayer increasedmore than tw-fold when using a rotating substrate. The increase was due to the enhancement of domain wall pinning effects caused by an
increase of surface roughness in the Si,N, underlayer.
The Si,Na underlayer surface prepared on a rotating
substrate was rougher than that on a stationary substrate, which may be due to the oblique incidence of
sputtered materials onto the rotating substrate.
1677-1685
Crystalline-electricfield (CEF) excitationsin the antiferromagneticheavy-fermion superconductorUPd,Al,
were studied by inelastic neutron scattering. UPd&
is an example of 5f-electron systems with a residual
line width which corresponds to the macroscopically estimated Kondo lattice temperature. However,
significant deviations from this suggest additional
inelastic conmbutions that persist up to T = 150 K.
This additional scattering could be due to CEF excitations or intersite magnetic correlations.
Long-Range Order and Magnetic Properties

of MnxPt1, Thin Films
K W . WIERMANandR D. K I R B Y , ~Magn.Magn. Muter.,
Superconductivity in Heavy-Fermion GF&Si,
1996,154,(l), 12-16
Thin films of Mn,Ptl., ( x = 0.18, 0.22, 0.25, 0.30,
0.34)prepared by magnetron sputtering onto quartz
substrates were annealed in vacuum for 1 h at 850C.
After annealing, XRD showed the 6lms to have the
CuAu cubic structure and be highly textured with
the (1 11) axis along the 6lm normal. The films displayed a high degree of long-range order, shown by
the ratio of the intensities of the superlattice (1 00)
and fundamental (200)XRD reflections.
R MOVSHOVICH, T. GRAF, D. MANDRUS,J. D. THOMPSON,

J. L. S M I T H and z. HSK, Phys. Rea B, 1996, 53, (13),
Growth of Ultrathin Pd Films on Al(001)

Surfaces
The Effect of Si/Ir CodepositionRatio on the

Ir SiliciddSi(100) Interface Roughness
V. SHUTIWANANDAN, A. A. SALEH, N . R. SHIVAPARAN

R.J.SMITH, s U t $ SCi., 1996,350, (1-3), 11-20
and
The growth mode and the interface structure of ultrathinPd films depositedon Al(OO1) surfaces were determined at loom temperature. Pd atoms intermixedwith
and displaced Al substrate atoms. The mixing continued for Pd coverages from 0-5 monolayers, when
a Pd metal film began to grow on the alloy surface.
X P S indicated that AlPd formed during mixing, followed by the formation of Pd metal.
Effects of Y2BaCu05and Platinum Additions

on the Unidirectional Solidification of
YBa2Cu307d
L. DURAND, D. DIERICKX, P. F&GNIER, 0.V A N DER BEST
and S. POISSOtiNET, Supercond Sci. Technol., 1996,9,

(4), 296296
The effects of 21 1 and/or Pt additions on the solidification ofYBaCu0 was studied. Mjxing the pure 123
powder with 20 wt.% very fine (1 pn) and regular
sized Pt 2 1 1 particles strongly increased the viscosity
of the peritectic liquid and resulted in a dramatic refinement in the dismbution of the 21 1 particles trapped
in the 123 ma& of the samples. Extra addition of 0.5
wt.% Pt further refined this dismbution.
Platinum Metals Rev., 1996,40,(3), 135-142
8241-8244
A superconductingtransition in the heavy-fermion compound CeRhSi, was discovered under hydrostatic pressure of > 9 kbar, near the critical pressure needed to
suppress antiferromagneticorder (T, (P = 0)= 36 K).
Superconductivity occurred at 350 mK. MagneticAC
susceptibility showed a diamagnetic response corresponding to 1% of perfect diamagnetism.
C. K. CHUNG andj. HWANG,
Muter. C h m . Phys.,1996,
43, (2), 191-194
The effect of the Si/Ir codeposition ratio on Ir silicide/Si( 100) interface roughness was studied on Ir
silicides grown on Si(100) by codeposition at Si/Ir
atomic ratios of 0, 1 and 2 at 450C under UHV.
Epitaxial I r S , grew on Si(100) as pure Ir was
deposited at all deposition ratios. The Ir,Sb/Si(lOO)
interface remained smooth, although intermixing
occurred during deposition, but at higher deposition ratios the Ir3SidSi(100) interface became rougher.
ElectricalConductivity and Superconductivity

of Metal Phosphides with Skutterudite-Type
Structure Prepared at High Pressure
I. SHIROTANI,T. ADACHI, K. TACHI, S. TODO, K. NOZAWA,
T. YAGI and M. KINOSHlTA,
PhyS. chem. sol&, 1996,
57, (2),211-216
Nip,, LaR~c,0s,P,~
( x = 0, 1,2, 3,4) and CeRwP,,
phosphides with skutterudite (CoAs,)-type structure
were prepared at around 1100C and 4 GPa using a
wedge-type cubic-anvil high pressure apparatus.
Superconductivity was observed in LaRu,P,,,
LaRu,OsP,, and I.~RLI~OS,P,~
at 7 K. The upper critical field of LaRaP,, was 3.65 T at 0 K.
135
Quantum Oscillations in the Layered

Perovskite Superconductor Sr2Ru0,
A. P. MACKFNZIE, S . R JULIAN,A. J. DIVER, G. 1. MCMULIAN,
M. P.RAY, G. G. LONZARICH, Y. MAENO, s. NISHIZAKI and
T. FWJITA, Phys. Rev. k t r . , 1996,76, (20), 3786-3789
A comprehensivestudy is presented of observed magneto-oscillatory phenomena in the normal state of

Sr,RuO,, which is the first layered perovskite superconductor (Tci 1 K) not based on Cu. All sheets of
the Fermi surface, includingthe large ones, have been
observed, thus permitting consistent correlation of a
number of physical properties. The observations are
compatible with a Fermi liquid, which may be liked
with coherentinterplane transport at low temperatures.
CHEMICAL COMPOUNDS
Size-Evolution Towards Metallic Behavior in
Nano-Sized Gold and Platinum Clusters as
Revealed by 19'Au Mossbauer Spectroscopy
F. M. MULDER, R. c. THIEL, L. J. DE JONGH and P. c. M.
Spectroscopic
and
Electrochemical
Investigation of Mixed-Valence Rh'-Rh"'
Complexes with Cyanide Bridge
T. V. MAGDESIEVA, S . I. GOREL'SKY, K. P. BUTIN, A. A.
BEZRUKOVA, V. S. KHANDKAROVA and YA. S . WGODSKII,
Izv. Akad. Nauk, Ser. Khim., 1996, (3), 726-731

New mixed valence Rh'-R"'' complexeswith cyanide
bridges were studied using electronic spectra and redox
potentials. Interaction between Rh atoms in the complexes is small (the ''tixed valences" case). Intervalence
transition from Rh' to Rh'" were not observed in the
7000-50,000/cm region. Some of the complexes in
the solid state have additional absorption bands in
diffise reflectance spectra due to the interaction of
the Rh(1) group orbitals of appropriate symmetry.
Synthesis and Characterization

Superstructured Rhodium Porphyrins
of
H. R. JIM&NEZ and M. MOMENTEAU, Inorg.
Chim. Acta,
1996,244, (2), 171-177
Three Rh "two-face'' hindered porphyrins were synthesised by the metallation of "basket-handle" porGUBBENS, NanoStructured Muter., 1996, 7 , (3),
phyrins in dimethylformamide, for example, [e269-292
BHP(C,,),Rh"'Q(H,O)]Cl, etc., where e-BHP(CI,),
1'17
Au Mossbauer spectroscopicstudies were made on = a5,15:p 10,20-bis [2,2'-(dodecamethy1eneoxy)the large Pt, cluster and four types of molecular Au,,
diphenyllporphyrinato dianion and L = dimethylamine.
clusters, with different types of ligands, using Ip7Au In these new neutral or cationic Rh porphyrins, the
produced by neutron activation. The ligands had a two faces of the porphyrin are protected by two chains
large effect on the charge densities at the surface atoms linked at the opposite phenyl rings. Studies of the
of the cluster cores. For the Ptm9compound, the inner derivatives of these porphyrins show different reduccore atoms had the same charge density at the nucleus ing tendencies, which follow in general the order for
as in the bulk metal. The inner core of the Ptlwclus- the axial ligand NH(CH,), > H,O or C1-.
ter is metallic, but the Au,, cluster is not.
on
a N~~ Oxoiridate(V)
NaSrrIrOn
.
ofthe SrSt06-~ype: The Activation of C-H Bonds via Ru-Ru Bond
Fission
s. m z m and H, M--BUSCHBAUM,
z.Namtforsch.
B. 1996., 51. f2). 225-228

,
X-ray studies were performed of single crystals of

NaSrlIrOs prepared by heating mixtures of NanOz,
SrO and Ir in closed Ag tubes. NaSr,IrO, crystallises
with trigonal (rhombohedral) symmetry in the space
group D,,"- R3c with a = 9.636(2), c = 11.556(3) A,
Z = 6, and is isotypic to compounds of the Sr,PtOa
type. The substitution of SrZ+by Na' in NaSrJrO,
resulted in an ordered metal distribution and in an
increase of the oxidation state from 11"
' to Ir".
A. J. BLAKE, P. J. DYSON, P. E. GAEDE and B. F. G. JOHNSON,
Inorg. Chim. Acta, 1996, 241, (2), 11-12

New metallacyclic cluster, Ru,(CO),(CUHs)(1) is produced in low yield by heating the RU,(CO)~(C~H,,)
cluster in heptane under reflux. In (l), the fission of
a Ru-Ru bond induced the cleavage of two C-H bonds
with the concomitant formation of two Ru-C (J bonds.
'H NMR spectra show the two H atoms lost in the
reaction are the most activated of those present on the
ligand, giving resonances at 0.88 and 1.56 ppm, which
are low compared with 7 ppm for the free ligand.
Synthesis and Spectral Studies of 1,3- A Chain Complex of Ruthenium(II,III) Cation

Diketonate Derivatives of ortho-Palladated Dimer Linked by a Nitroxide Radical,
[Ruz(OzCCMe,),(NITPh)] n(BF,)n (NITPh =
a-Arylalkylamines
2-Phenyl-4,4,5,5-tetramethyl-4,5-dihydroV. V. DUNINA, 0. A. ZALEVSKAYA, S. P. PALII, D. V.
1H-imidazolyl-1-oxy-3-oxide)
ZAGOREVSK~and YU. S . NEKRASOV, Izv. Akad. Nauk,
M. HANDA, Y. SAYAMA, M. MIKURIYA, R. NUKADA, 1.
Ser. Khim., 1996, (3), 733-740
Acetylacetonato derivativesof a series of orzho-palla- HIROMITSU and K.KASUGA, Chem. Lett. &n., 1996,
dated secondary and tertiary a-arylalkylamines were (3), 201-202
prepared and characterised. An unusual rearrange- The above Ru chain complex was characterised by
ment involving migration of an H atom from the alkyl the X-ray analysis, showing a structure with the alteraminoalkyl group to the Pd atom leading to a hydride nated alignmentof S = 3/2 (Ru(II,IQ core) and S= 1/2
intermediate and followed by PdH elimination was (NITPh). The magnetic moment decreased monoobserved. This may be due to isomerisation of qz-O',O- tonically with decreasing temperature. This chain
coordinated w e t o n a t e ligand into the ql-C-bonded complex has a paramagnetic dimetal centre with a
diketonyl form, to give the unsaturated metal centre. metal-metal bond linked by the nitroxide radical.
136
ELECTROCHEMISTRY
A New SuccessiveSystem for Hydrogenation

of Styrene Using a Two-Compartment Cell
Electro-oxidation of C1 Molecules at Pt-Based Separated by a Pd Sheet Electrode
Catalysts Highly Dispersed into a Polymer c. IWAKURA, T.ABE and N.mom, 3: Elecmchem. Sac.,
Matrix: Effect of the Method of Preparation 1996,143, (4), L71-L72
w. T. NAPPORN, H. LABORDE, J.-M. ~ G E and
R c. LAMY,
J. Electroanal. Chem., 1996,404, (l), 153-159
Highly dispersed Pt-based electrodes modified with
Ru andor Sn inserted in a conductingpolymer matrix
exhibited weak poisoning effects compared with pure
Pt particles. The Pt-Ru alloy was the most promising
catalyst for the electro-oxidationof MeOH, while PtSn electrodes gave a very significant negative shift to
the oxidation potentials during electro-oxidation of
formaldehydeand formic acid. An important decrease
in poisoningwas found mainly with Pt-Sn electrodes,
but also with Pt-Ru and Pt-Ru-Sn electrodes.
The Electrooxidation of Formaldehyde on

Pt(100) and Pt(ll0) Electrodes in Perchloric
Acid Solutions
P. OLIVI, L. 0. S.BULHdES,J.-M. L k G W F.HAHN, B. BEDEN
and C. IAMY, Elecnochim. Acta, 1996,41, (6), 927-932
Studies of the electro-oxidation of formaldehyde on

Pt( 100) and (1 10) electrodes in a perchloric acid
medium showed both undergo two oxidation processes
involving either methylene-glycol oxidation or adsorbed
CO formation. The Pt(100) electrode is more active
for the methylene-glycol oxidation. The CO species
were adsorbed linearly on both electrode surfaces, but
multibonded and bridge bonded CO forms were only
present on the Pt( 100). The adsorbed CO species
block the surfaces during methylene-glycol oxidation,
with Pt(ll0) being more blocked than Pt(100).
Hydrogen Evolution Reaction in Alkaline

Solution. Catalytic Influence of Pt Supported
on Graphite vs. Pt Inclusions in Graphite
A new successive system for the hydrogenation of

styrene using a Pd sheet electrode is reported. The
activated H atoms are electrochemicallyproduced at
the front side of the Pd sheet electrode and supplied
through it to be used for hydrogenation at the back
surface of the Pd sheet electrode. Only ethylbenzene
was produced, and the production rate depended on
the applied current. The current efficiency of > 93%
occurred at an applied current of 10 mA.
Voltammetric Study of the Immobilizationof

Palladium at the Surface of Carbon Paste
Electrodes
LUBERT, M. GUITMANN
and L. BEYER,
Electroandysis, 1996,8, (4), 32&325
Cyclic voltammetric studies were performed of Pd
immobilisation at the surface of unmodified C paste
electrodes. During pretreatment at 0 V, Pd was bound
at the surfaceof the C paste, and the amount of immobilised Pd depended on the composition of the solution, polarisation time, electrode potential and stirring. During an anodic scan, the surface-bound Pd
was oxidised at + 0.6 V and the well-shaped peaks
could be utilised for the determination of the immobilised Pd. The detection limit was 5 x 10-6MPd2'
after 5 min polarisation at 0 V with stirring. Pd and
H can be "deposited" simultaneously at the C paste
surface through cathodic polarisation.
K.-H.
Rapid Oxidation of Ru(NH,),J'by Os(bpy)?

within Nafion Coatings on Electrodes
M. SHI and F. c. ANSON, Langmuir, 1996, 12, (8),
2068-2075
When Ru(NH,)S)' (1) and Os(bpy)? (2)reactants are
incorporated in Nafion coatings on electrodes, the
1996, 143, (3), 919-926
oxidation of (1) by (2), which is normally a very slow
Electrocheinicalbehaviour of Pt having graphite pow- process, can proceed much more rapidly, especially
ders bonded by polymerised LaPO, was studied for with Nafion coatings that are not fully hydrated. The
the HER in 1 M KOH solution. Pt-supported elec- Ru(NH,)? is oxidised to R u m at a rate that is first
trodes, Pt(s)/C/LaPO, (1) were more active than those order in Ru(NH,)S)' and Os(bpy)?, and inverse first
containing Pt inclusions in graphite, Pt(i)/C/LaPO,
order in H'. The higher reaction rate obtained upon
(2).In high-current-density conditions of 0.25 Nanz, incorporation of the reactants into Naiion results ftom
(2)was stable while (1) disintegrated after 24 h.
their higher concentrationsrather than &om enhancement in the intrinsic redox reactivity of either cation.
J. FOURNIER, L. BROSSARD, J.-Y. TILQUIN, R. C 6 T & J.-P.

DODELET, D. GUAY and H. M&NARD, J. E l e c m c h . Sac.,
Fabricationof Ptl(Ta,O,+Pt) Coated Titanium

Electrodes Using Combination of Partial
Thermal Decomposition and Electrolytic
Reduction of Pt and Ta complex
Y. KAMEGAYA, J. SAITO,H. KOBAYASHI, M. OKWAMA and
T. MITAMURA, DenkiKagaku, 1996,64,(2), 138-142
Electrochemical Behavior of the RuODiO,

Anodes during the Electrolysis of Sea Water
c.LIANG and Q. GU, Corm. Sci. h t . Technol. (China),
1996, 8, (2), 125-129
Studies of the electrochemicalbehaviour of the anode

RuOJTiO, during the electrolysis of sea water showed
ricated, to protect the Ti substrate from corrosion, by that use of the anode could improve current effipartial thermal decomposition (1) and electrolytic ciencies and decrease energy consumption. The best
reduction of Pt(NOz),(NH3),,and (1) of Ta(OC2Hr)s. results were obtained at current densityof 100 &anz
The interlayer is amorphous Ta20, and Pt, with a Pt and electrode gap of 5 mm. The cathode was electop layer. It has excellent stability during anodic O2 trochemically protected at potentials from - 820 to
evolution in HzSO,, high conductivityand durability.
-1450 mV (SCE).
A three-layered Pt/(Taz05+Pt)/Tielectrode was fab-
137
Investigation of the Formation of RuO,-Based

Mixed Oxide Coatings by Secondary Ion Mass
Spectrometry
ELECTRODEPOSITION AND
SURFACE COATINGS
and A.
J. Murer. Chem., 1996,6, (4), 567-57 1
The evolution of a Ru0,-TiO, film electrode with
temperature was studied using a coating mixture prepared on a Ti support from an isopropylalcohol solution of hydrated Ru chloride and Ti diisopropoxide
bispentane-2,4-dionate precursors. Concentration
depth profiles monitored film evolution and identified surface segregation phenomena resulting from
the increased metal dispersity.
Characterization of a Colloidal Pd(II)-Based

Catalyst Dispersion for Electroless Metal
Deposition
S. DAOLIO, J. KRIST6F, C. PICCIRILLO, C. PAGURA
DE BATTISTI,
PHOTOCONVERSION
The Role of Acidity in the Photoreaction of
Carboplatin
w. LIU, Y. YANG, H. XIONG and z. QUE, Precious Met.
(China), 1996, 17, (l), 19-22
Photochemical studies of acidic solutions of carboplatin on irradiation at 313nm showed that the photolytical product is C~~-[P~(NH,),.(H~O)~]+
and the
quantum yield is 0.89. Acidity is a major factor in the
photoreaction of carboplatin and the mechanism is
discussed.
Vibrational Sidelines in the Localized

3MLCT Emission of [Ru(bpy),(bpz)12 in
[Zn(~py)3](cI04)2(bpy = 2 4 -Bipyi&e, bpz
= 2,2 -Bipyrazine)
W. J. DRESSICK, L. M. KONDRACKI, M:S. CHEN, S. L.

BRANDOW, E. MATlJEWdandJ.M. WVERT, colloid surf:
A:Physicochem. Eng. Aspects, 1996,108, (l), 101-1 11

An aqueous Pd(I1) dispersion for the selective electroless deposition of Ni at ligand-bearing surfaces,
was prepared by hydrolysis of PdCL, at pH 5 in NaCl
solution. The dispersion comprised anionic and
uncharged Pd(I1) species, from monomeric to colloidal, with colloidal species starting the electroless
metal deposition. The colloidal catalysts have a diameter 4-53 nm, with an average size of 30 f 12 nm.
Electroplated Palladium Coating as a Nickel

Migration (Thermal) Barrier
J. K. m,J. s. RUSSO and E. ANTONIER, Pkzt.surf: Finish.,
1996, 83, (3), 64-67
Ni-Co plated chip carriers were coated with an acid
Pd strike and electrolyticPd deposits, using three different plating combinations: Ni-Co/Au (Pd strike),
Ni-Co/Pd and Ni-Co/Pd/Au. Ni-Co/Au plated carriers were the standard. The tested samples showed
equivalent or better Ni migration and solderability
than the standard, that is, less than 10 at.% Ni migration and nearly 100% solder flow.
APPARATUS AND TECHNIQUE

L. WALLACE and E. KRAUSZ, J. phys. Chem.,
1996,100, (1 l), 4390-4394
The luminescence spectrum of [R~(bpy)~(bpz)]
(1) Flow Injection Amperometric Detection of
and [Ru(bpy-d&(bpz)lZ+complexes in the host Ammonia Using a Polypyrrole-Modified
[Zn(bpy),](ClO,), (2) was studied and sidelines asso- Electrode and Its Application in Urea and
ciated with the spectator bpylbpy-4 ligands were iden- Creatinine Biosensors
tified over the entire vibrational frequency range. M. TROJANOWICZ, A. LEWENSTAM, T. KRAWCZYtkKI, V.
Although the lowest excited MLCT states in Ru KRAWCZYK, I. LAHDESMAKI and w . SZCZEPEK,
diimine systems are localised, the coupling in the Electroanalysis, 1996,8, (3), 233-243
MLCT excitationsis 3 4 orders of magnitude larger. Amperometric NH, detection, using an anodically
Dominant sidelines reported earlier for (1) in (2) polarised Pt electrode, modified with PPy, was used
are caused by contamination by [O~(bpy)~(bpy-&>]. in biosensors. NH, detection in a flow injection system with 5 100 ph4 of analyte at a detection limit of
Photosensitization of Nanocrystalline 0.6 pM was used to detect urea and creatinine by
Semiconductor Films. Modulationof Electron immobiling urease and creatinine iminohydrolase,
Transfer between Excited RutheniumComplex respectively, at the PPy surface. A biosensor of very
and SnOINanocrystalliteswith an Externally low sensitivity was obtained by urease entrapment
in the PPy layer during electropolymerisation.
Applied Bias
P. v. KAMAT, I. BEDJA, s. HOTCHANDANI and L. K.
Effect of Electrode Materials on the Sensitive
PATTERSON, 3. Phys. Chem., 1996, 100, (12),
Properties of the Thick-Film Ceramic
49004908
Humidity Sensor
The charge injection from excited Ru(bpy),(dcbpy),
Ru(II), into SnOZnanocrystallites was studied by in w . QU, Solid Scare Ionics, 1996, 83, (3, 4), 257-262
A thick-film humidity sensor with excellent stability
situ specnoelectrochemicalmeasurements. Laser flash
photolysis of Ru(II)-modified SnO, nanocrystalline was produced by depositing a humidity sensitive layer
film was used to record the transient absorption spec- between two metal electrodes on an AlzO, substrate.
tra at different applied potentials. The yield of elec- The sensor response depended on the sensing layer
mn transfer product, R u m , decreased as the applied and the properties of the electrode material. Pt elecbias was switched to negative potentials. At a bias of trodes gave higher sensitivity over the whole humidity range, and faster response than AgPd electrodes.
-0.7 V, Ru(II)* was the only observed transient.
H. =EN,
138
Composite PdlTa Metal Membranes for

Hydrogen Separation
Synthesis and Characterization of Sol-Gel

PtlTiO, Catalyst
J. Membrane
Sci., 1996, 111, (l), 123-133
A composite metal membrane was fabricated by
vapour deposition using 13 pTa foils cleaned by ion
milling, then coated with 1 p of Pd metal on each
side. The membrane of area 2 an', gave exceptionally
high H gas fluxes from 18.7 standard cm3/min(sccm)
at 300C to 27.4 sccm at 365C with a H differential pressure of 355 torr. The deposited Pd films
were oriented along the (1 11) crystal axis.
E. S h C H E Z , T. L6PEZ, R &MEZ, BOKHIMI, A. M O W S

and 0 . NOVARO, J. Solid State Chem., 1996, 122, (2),
N. M. PEACHEY, R C. SNOW and R C. DYE,
HETEROGENOUS CATALYSIS
Deep Hydrodesdfurization of DBT and Diesel
Fuel on Supported Pt and Ir Catalysts
R NAVARRO, B.PAWELEC, J. L G. FIERRO, P. T. VASULEVAN,
J. F. CAMBRA and P. L ARIAS, Appl. C a d . A: Gen., 1996,
137, (2), 269-286

Deep hydrodesulphurisation (HDS) of dibenzothiophene (DBT) and diesel fuel (with 0.08 wt.% S) was
performed using Ptl- and Wamorphous SiO,-Al,O,
(ASA) and on a stabilised HY zeolite. The normalised
activities of PtlASA and PdHY catalysts were better
than those of the Ir catalysts, with the HDS being
dominant over hydrogenation. In HDS of diesel fuel
(at 623 K), both Pt catalysts were a little more active
than a commercial Co-Mo/Alz03catalyst. The normalised activity for HDS of DBT (593 K) increased
as: PdHY> WASA >>Ir/HY >Ir/ASA, and the HDS
of diesel fuel (623 K) increased as: Pt/HY>>Pt/ASA
>> W H Y > IrlASA.
Regioselective Hydrogenation of Alkenes over

Pt-Loaded Zeolite BEA
309-3 14
PvTiO, catalysts with 1.O wt.% Pt were prepared in
a one-step operation by the sol-gel technique with
Ti(OBut)r and Pt acetylacetonate,without any reduction of the sample in H,. The fresh samples had three
nanophases: rutile (the majority), anatase and Pt. Pt
promoted the formation of rutile, either due to the
presence of an intermediate PtO, phase, having the
rutile structure, or to the Pt-catalysed dehydroxylation of anatase. Pt atoms do not enter into the crystalline structure of rutile, despite both PtO, and rutile
having the same crystalline structure.
Crotonaldehyde Hydrogenation over

Bimetallic Pt-Sn Catalysts Supported on
Pregraphitized Carbon Black. Effect of the
SdPt Atomic Ratio
F. c o m a A. SEW~L.~~?DA--ESCIUBANO, J. L G. FJERRO and
F. RODR~GUEZREINOSO, Appl. Catal. A: Gen., 1996,
136, (2), 231-248

Three bimetallic Pt-SdC catalysts, prepared by successive impregnation of pregraphitised C black with
an aqueous solution of hexachloroplatinic acid and
Sn(I1) chloride, were studied during crotonaldehyde
hydrogenation. When Sn was added to the samples,
the amount of surface Pt was greatly reduced. Both
Pt' and Pt"were detected by X P S in the fresh bimetallic catalysts. After reduction in flowing Hzat 623 K,
Pt was completelyreduced to metal, and some Sn was
reduced to Sno,possibly allowing Pt-Sn alloy formation. Catalytic activity for gas phase hydrogenation of
crotonaldehyde was greatly improved by Sn.
E. J. CREYGHTON, R A. W. GROTJNBREG, R. S. DOWNING

and H. VAN BEKKUM, J. Chem. Soc., Faraday Trans.,
A Pt-Rh Synergism in PtlRh Three-Way

catalysts
1996,92, (5), 871-877

The hydrogenation of dec-1-ene (1) and (E)-dec-5ene (2) was studied over Pt/Na-BEA and non-zeolitic
Pt catalysts. Under specific conditions using m a BEA, (1) is hydrogenated 18 times faster than (2),
whereas the ratio is only 2 for Pt on non-microporous supports. Compared with Pt/Na-BEA, Ptl
amorphous mesolmacroporoussupport shows a higher
activity in the catalytic hydrogenation of (1) and (2)
but a much lower regioselectivity. The hydrogenation
over Pt/Na-BEA deviates from zero-order kinetics.
Z.HU, Chem. Commun., 1996, (7), 879-880

Performances of Pt, Rh and Pt/Rh catalysts were
assessed after ageing in exhaust to mimic in-use catalyst operation. The activity of the Pt/Rh catalyst was
about one order of magnitude higher than either a
Pt or an Rh catalyst for HCICOINO three-way conversions. This high activity of the PtRh three-way catalyst is attributed to a R-Rhsynergism.The W A l
catalyst also gives HC/CO conversionsof 50% at temperatures 70 K lower thanthe WAI catalyst and lower
than the WAl catalyst by 100 K.
Kinetic Modeling of CO Oxidation on PtlCeO,

in a Gradientless Reactor
M. A. SHALAFJI,B. H. HARJI
and c. N. KENNEY, 3 Chem.
Structure and Catalysis of a SiOl-Supported

Gold-Platinum Cluster [(PP~)Pt(PPhAu),]
Tech. Biotechnol., 1996, 65, (4), 317-324

Pt/CeOz was studied in order to understand the promoting effects of CeO, in the CO oxidation reaction, at 100-170C. At low concentrations of reactants,Pt/CeOzexhibitedmultiple steady states, similar
to the multiplicity behaviour of F't/Alz03.CeO, lowers the activation energy for CO oxidation, increases
the activity of the reaction by being a good 0, store
and suppresses the usual CO inhibition effect.
Y. YUAN, K ASAKURA, H. WAN, K TSAI and Y. IWASAWA,
Platinum Metals Rw., 1996,40, (3)
(NO,),
C h m . ZAZ. Jpn., 1996, (2), 129-130
A Pt catalyst [(PPh3)Pt(AuPPh3)6](N0,)z
(l)/SiOzwas
very active for H,-D, equilibration with a T O F of
29.8/s, but had low activity for ethene hydrogenation
and CO oxidation at 303 K.Pt atoms bonded to Au
atoms in the cluster. The cluster fixmework of (l)/SiOz
was stable during the reactions at 303 K. The number of Au-Pt bonds fell after heat treatment.
139
The Shape-Selectivity of Activated Carbon

Fibers as a Palladium Catalyst Support
H.JIN, S.-E. PARK, J. M. LEE and S.K. RYU,
Carbon, 1996,
34, (3), 429-431
Activated C fibre (ACF) was used as a shape-selective catalyst support for Pd. Pd was depositedon pitchbased ACF and was used as the catalyst in the liquidphase heterogeneous hydrogenation of olefinic C,
hydrocarbons. As the adsorption capacity increased,
the pore size distribution became wider, and mesopores and wider micropores increased. HNO, treatment and Pd loadings did not greatly affect the types
of adsorption isotherm. For 1-hexene, the hydrogenation rate was a function of mean pore radius: the
reaction does not occur at a mean pore radius of <
0.9, but for > 0.9 the reaction rate increased considerably. Shape-selectivity occurs inside the pores.
Liquid Phase Hydroformylation of Ring

Substituted Styrenes Catalyzed by Rh-B and
Rh-Zn-B Systems Supported on Silica
M. LENARDA, R. GANZERLA, S. PAGANELLI, L. STORARO
and R. ZANONI, J. Mol. Catul. A: Chem., 1996, 105,
(3), 117-123
Rh based catalysts/Si02 were prepared by low temperature reduction of the preadsorbed salts with
NaBI-h and Zn(BH,),. A remarkable B and Zn surface enrichment was observed from ESCA data in
both catalysts. Both catalysts were active in the hydroformylation of liquid phase ring-substituted styrenes.
The resulting reaction was really heterogeneous as no
catalyst leaching occurred. The chemoselectivitywas
always close to loo%, and regioselectivity appeared
to be controlled by the nature of the ring substituents.
Synthesisof CyclopentanoneDerivativea with

Polystyrene-Supported Cyclopentadienyl
Rhodium Catalysts
D. P. DYGUTSCH and P. EILBRACHT,
Tetrahedron, 1996,
52, (15), 5461-5468
A polystyrene-supported q5-cyclopentadienylRh catalyst was applied to two different methods of cyclopentanone synthesis. The synthesis of substitued cyclopentanones was performed either by hydrocarbonylative
cyclisation, starting from 1,4-dienesor from ally1vinyl
ethers via tandem Claisen reanzmgement, and intramolecular hydroacylationof the 4-pentenal intermediates.
The polymer-attached CpRh(cod) complex was a very
efficient and reusable hydroformylation catalyst.
Ruthenium Catalyst Supported on CeO, for

Ammonia Synthesis
Y.NIWAandK-I.m, Chem. Lett.Jpn.,1996, (l), 3-4
Lanthanide oxides, Sm,O,, La,O,,especially CeO,,
were more effective, when supporting Ru catalysts,
rather than being a dopant during NH,synthesis. The
activity of Ru/La,O, catalyst was superior to other
metal oxide-supported Ru catalysts, such as RdMgO.
The activity, Ru dispersion, BET surface area and the
amount of H consumption by Ru/CeOzdepended on
H2treatment, thus suggesting a SMSI phenomenon.
Partially reduced CeOzdonated electronsto Ru atoms,
which then formed the active sites.
A Novel Basic Alkaline-Earth ZeoliteSupported Ruthenium Catalyst for Ammonia

Synthesis
c. T. FISHEL, R. J. DAVIS and J. M. GARCES, Chem.
Commun., 1996, (3,649-650
Studies of the promotional effect of alkaline-earth
cations on the catalytic activity of Rdzeolites during
NH,synthesisshowed an increase in the reaction rates
that exceeds those for analogue catalysts containing
only alkali-metal cations. The Ru clusters were supported on basic zeolite using as a starting material
KX, CsX, CaX, BaX and MgO. Ru/BaX and RdCaX
catalysts were three times more active than RdCsX;
this is the highest value for zeolites in NH, synthesis.
Carbon Monoxide Hydrogenation on

Supported Manganese-Ruthenium Catalysts
C d . A: Gm.,
1996,136, (2), 105-111
CO hydrogenationover 6.3% Mn-2.5% RdA120,catalyst was studied in a flow system with a dserential
fixed-bed reactor operating under atmospheric pressure at 553-613 K, H,:CO = 1:3 and space velocity
5 100-27,600 cm/gh. Modification with Mn resulted
in a shift of the product distribution to lower olefins.
The activity and selectivity of the catalyst changed
atbelow and above 573 K. It is suggested that atmelow
573 K, monolayer C deposits and > 573 Kmultilayer
C deposits affect the performance of the catalyst.
T. TERCIOGLU andJ.F. AKYURTLU, &l.
Hydrogenation of Citral and Ciamaldehyde

over Bimetallic Ru-Me/Al,O, Catalysts
G. NERI, L. MERCADANTE, C. MILONE, R. PIETROPAOLO
and S . GALVAGNO, Mol. catal. A: Chem., 1996,108,
(l), 41-50
Hydrogenations of citral and cinnamaldehyde were
studied over Ru-Me/Al,O, catalysts, where Me = Ge,
Sn or Pb. Two series of catalysts were prepared by
using the controlled surface reaction (CSR) technique
(RuEC series) and the more conventional co-impregnation method (RuNI series). Addition of Ge increased
the catalytic activity of the RuEC series, but had no
effect on RuNI series. Addition of Sn universally
increased both activity and selectivity. The Pb present
did not modlfy the selectivity and slightly decreased
the catalytic activity on RuNI series samples.
HOMOGENEOUS CATALYSIS
Intramolecular Heck-Type Reactions in
Aqueous Medium. Dramatic Change in
Regioselectivity
S. LEMAIRE-AUDOIRE, M. SAVIGNAC, C. DUPUIS and J:P.
GE-T,
Tetrahedron Lett., 1996,31, (12), 2003-2006
Intramolecular Heck-type cyclisations promoted by

P d ( 0 A c ) m M S and PdClJrpPTS catalytic systems,
in CH,CN/H,O medium, are reported. The cyclisations were efficiently performed in aqueous medium.
Unexpected endo selectivity was observed rather than
the usual ex0 process, the reaction reversing in favour
of the endo cyclised compounds. Either endo or exoring closure can be obtained from the same substrate.
140
Mild hide-Mediated Palladium-Catalysed

Cleavage of Allyloxycarbonyl Protected
Alcohols in Aqueous Media
Chem. Res. (s), 1996,

(113 4 6 4 7
The deprotection of allyloxycarbonyl-protectedalcohols was efficiently performed under neutral conditions using Pd(OAc),-tppts catalyst in MeCN-H,O,
in the presence of NaN,as ally1 scavenger. The deprotection reaction proceeded smoothly with alloc-primary and alloc-secondary alcohols, giving quite good
yields. The H,O-soluble catalyst can be easily reused
without the addition of more nucleophile.
S. SIGISMONDI and D. SINOu, J.
An Improved Procedure for the Synthesis of

Substituted Acetylenes from the Reaction of
Acetylene Gas with Aryl Iodides under
Palladium-CopperCatalysis
M.PAL and N. G. KUNDu,J. Chem. soc., perkin Trans.
I, 1996, (59,449-451
The use of dimethylformamide @MF) as a solvent
promoted the Pd-Cu catalysed reaction of acetylene
gas with aryl iodides in a closed system to give disubstituted acetylenesin fair to excellentyields. The reaction was carried out in the presence of [Pd(PPh,),] Ch,
E t a and CuI in Dh4F in acetylene gas. When chloroform was used as the solvent, mixtures of monoand disubstituted acetylenes were produced; some of
these have biological interest.
Synthesis and Characterization of

Poly(ethynyltrimethyIsi1ane) Containing
Pd(II) Coordination Sites
M.v. RUSSO, A. FURZANI, M.cuccu and G. POLZoNEm,
Polet,
1996,37, (9), 1715-1722
Polymerisation reaction of ethynyltrimethylsilane
(HC=C-Si(CH;),) are reported in the presence of the
bis(acetiy1ide) complex {Pd[C=C-Si(CH3)3],(PPh,)z}
in 1:lOO; 1 5 0 and 1:25 catalyst : monomer ratios.
The catalyst plays different roles, such as activation
by Pd of the mple CIC bond of the monomer and
insertion into the Pd-C a-bond with growth of the
polymer chain; oxidation of PPh, to OPPh, which can
be released leaving free co-ordination sites on Pd followed by crosslinking with the C=C bonds of neighbouring polymer chains; and in the presence of
NH(C,H5),, the C-Si bond is activated followed by
substitution of some Si(CH,), groups with N(C,H,),.
Direct Formation of Alcohols by

Hydrocarbonylation of Alkenes under Mild
conditions Using Rhodium Triaikylphosphine
catalysts
J. K.M A C D O U G U M.C. SIMPSON, M.J. GREEN and D. J.
COLE&AMILTON,J.
Chem. SOC.,
Dalton Trans., 1996,
(6)y 1161-1172
The hydroformylation of hex-1-ene to heptanal and
2-methylhexanalin toluene w a s catalysed by the complex m ( P E t , ) , ] , while in tetrahydrofuran significant amounts of heptanol and 2-methylhexanol were
formed, especially over long reaction times. In protic solvents only alcohols were produced even after
short reaction times. The reactions were very rapid
and occurred readily with alkenes. The highest rates
were observed for ethene (54,000 turnoversh) and
the products were always alcohols.A new mechanism
for this direct hydrocarbonylationis proposed.
Catalytic Alkane Dehydrogenation by

1rClH2(PPri&: Evidence for an Alkane
Associative Mechanism
and c. M.JENSEN,OrganometaUics, 1996, 15,
(6), 1532-1534
The dehydrogenationof alkanes to alkenes was catalysed by IrClH,(PW,), in the presence of the H acceptor, tert-butylethylene, at 15OOC. Mechanistic studies, includinglabelllng experiments with IrClD2(PW3)z,
showed that reversible co-ordination and hydride
migration to ten-butylethylene is facile and that the
slower, subsequent elimination of ten-butylethane
required prior co-ordination of alkane.
J. BELLI
Ru-Catalyzed Hydrogenolysie of ChiralAUylic

and Propargylic Cyclic Carbonates: Synthesis
of Optically Active (Q-Allylic and Allenic
Alcohols
s.-KKANG,D.-Y. KIM,H.-S.RHO,S.-H.YOON~~~P.-S.
no,
Spth. Commun., 1996,26, (8), 1485-1492
Optically active (E)-allylic, (EYE)-dienylicand allenic
alcohols were synthesised with excellent regioselectivity by RuH2(PPh3),(1) catalysed reductive cleavage of chiral allylic cyclic carbonates with NH,formate. Also, hydrogenolysis of propargylic cyclic
carbonates by (1) afforded only allenic alcohols.
FUEL CELLS
Hydroformylation of Unsaturated Alcohols

Catalyzed by Rh(acac)(CO), Modified with
Different Phosphorus Ligands
The Chemical State of Sulfur in CarbonSupported Fuel-Cell Electrodes

K. E.SWIDER and D. R ROLISON, 3 Electrochem. Soc. ,
E.WOLSZCZAK and J. J. ZI~LKOWSKI,

N m J . Chm., 1996, 20, (3), 365-370
The activity of Rh(acac)(CO), catalysts modified with
mono- and diphosphorus ligands of different electronic and steric properties was studied during hydroformylationof unsaturated alcohols at 6040C under
10 atm HJCO = 1. The reaction of the 3-buten-201 and 1-octen-3-01 yielded the cyclic 2-hydroxy-5methyltetrahydrofuran and 2-hydroxy-5-pentyltetrahydrofuran, respectively. Ph2P(CH2),PPh2and
P(O-m-MeCsH,), gave the highest catalytic activity.
1996,143, (3), 813-819

The chemical state of S in W C elecwcatalysts, using
vulcan C, was studied by measuringits oxidation state
by XPS during the preparation of a mock fuelcell electrode to find if the S from the C affects the
electrocatalyst. Pt catalytically oxidised some of the
covalent S in the vulcan C to sulphate when H,O, heat
and strong physical contact between Pt and C were
all present. However, most of the zero-valent S
remained in the C after treatment, without any initial
contact with Pt, so may be a source of Pt poisoning.
A. M.TRZECIAK,
Platinum Metals Rm., 1996,40, (3)
141
Analysis of Reaction Kinetics for Carbon

Monoxide and Carbon Dioxide on
Polvcrvstalline PlatinumRelative to Fuel Cell
OGraiion
R. J. BELLOWS, E. P. MARUCCHI-SOOS and D. T. BUCKLEY,
Ind. Eng. Chem. Res., 1996,35, (4), 1235-1242

Hydrogen can be produced in a polymer electrolyte
fuel cell by reforminghydrocarbons or alcohols. Such
H, contains CO and C O , (COX) impurities which
adsorb onto the Pt anode electrocatalyst,reducing the
efficiency for H,electro-oxidation. Studies showed
that the rate of CO electro-oxidation is an important factor in determining the CO tolerance of Pt
anodes. It is suggested that for CO tolerance, all CO
in the feed must be effectively consumed during electro-oxidation at low potentials; CO adsorption fluxes
will be much faster than CO, electroreduction on Pt.
Work Function Variations and Oxygen

Conduction in a Pt I ZrO,(Y,O,) I Pt Solid
Electrolyte Cell
N. G. TORKELSEN and S. RAAEN, A@l. s U l $
sci., 1996,
93, (3), 199-203

The working electrode in a Pt I ZrO,(Y,O,) IPt solid
electrolyte cell was studied by photoelectron spectroscopy in UHV, and changes in the electrode work
function were correlated with the 0 ion transport
through the cell. The change in work function was
independent of the cell temperature, when the cell
operated as an 0 conductor. Negative 0 species at the
working electrode during 0 pumping were indicated.
CHEMICAL TECHNOLOGY
Preparation of PdlCeramic Composite
Membrane. 1. Improvement of the
Conventional Preparation Technique
Membrane sci.,
1996, 110, (2), 257-260
An improved method of making Pd/ceramic composite membranes has been developed. Thin Pd films
were deposited on the surface of a porous ceramic
substrate by the conventionaland the improved electroless plating technique. The improved method preseeds Pd nuclei in a new way: Pd modified by yAlOOH sol is deposited on the surface of the porous
A120,disk support by a slip-casting process, calcined in
air, then the Pd ion in the top layer is reduced to metallic Pd in H2for 2 h at 400C. The Al,O, membrane +
Pd nuclei is then elearolesslyplated in a Pd bath.
A. LI,G. XIONG, J. GU and L. ZHENG,
Sonochemical Preparation of Ultrafine

Palladium Particles
K. OKITSU, H. BANDOW and Y . MAEDA,
Chem. Muter.,
1996, 8, (2), 315-317

Ultrafine Pd particles were prepared by using ultrasound to reduce tetrachloropalladateions in aqueous
solutions. Stable fine particles of Pd were readily produced in the presence of a protective agent, such as a
surfactantor a H,O-soluble polymer. The Pd particles
obtained were very fine and their sizes had only a narrow dismbution in the range of several nanometres.
ELECTRICAL AND ELECTRONIC

ENGINEERING
PtmZTln-SrTiO, Ferroelectric Memory Diode
K.GOTOH, H.TAMIJRA, H. TAKAUCHI and A. YOSHIDA,
Jpn.J. Appl. Phys., 1996, 35, (lA), 39-43

A non-volatile ferroelectric memory was fabricated
from vertical metal-ferroelecaic-semiconductor
diodes
with simpler structure than a ferroelecmc random
access memory (FRAA4) cell. It operates at a lower
voltage than metal ferroelectric semiconductor field
effect transistors or flash memories. The correct nonvolatile and non-destructive memory read-outs were
shown with the Pt/PZT/n-SrTi0,diode. The write
voltages were - 5 V to write a logic 0 and > 2.5 V
to write a logic 1. The read voltage was 0.8 V.
Material and Electrical Characteristicsof Iron

Doped Pt-InAIAs Schottky Diodes Grown by
LP-MOCVD
K. HONG, D. PAVLIDIS and F. S&JALON,J.
Elecmm.M u m ,
1996, 25, (4), 627-632
The effect of Fe doping on elecmcal properties and
on noise characteristics of devices was studied using
Pt-Schottky diodes fabricated on undoped and Fedoped InAlAs. Fe-doped InAlAs showed a Lorentzian
component in the noise spectra not found in undoped
materials. An activationenergy of 0.77 eV was found
for traps due to Fe incorporation, using temperature dependent low frequency noise measurements.
Barrier Characteristics of PtSilp-Si Schottky

Diodes as Determined from I-V-T
Measurements
P. G. MCCAFFERTY, A. SELLAI, P. DAWSON and H. EIABD,
Solid-state Electron., 1996, 39, (4), 583-592

The current-voltage-temperature characteristics of
PtSVp-Si Schottky barrier diodes were measured at
60-1 15 K. Deviation of the ideality factor from unity
below 80 K was modelled using the so-called Toparameter with To= 18 K as an inhomogeneous Schottky
contact. A mean barrier height at T = 0 K,
= 223
mV, with an assumed Gaussian dismbution of standard deviation, 0, = 12.5 mV was determined.
TEMPERATURE MEASUREMENT
Progress on Fabrication of Iridium-Gold
Proximity-Effect Thermometers
J. HOHNE, G. FORSTER, C. ABSMAIER, P. COLLING, S.
COOPER, F. V. FEILITZSCH, P. FERGER, J. IGALSON, E.
KELLNER, M. KOCH, M. LOIDL U. NAGEL, F. PROBST, A.
RULOFS and w. SEIDEL, Nwl. Insm Methods, Phys. Res.
A , 1996,370, (l), 160-161
Ir-Au proximity-effect bilayers with critical temperatures 20-1 00 mK were made as superconducting
phase transition thermometers for low temperature
calorimeters. Film thickness for the Ir and Au films
is controlled during evaporation to f 3% and varies
< 15 A at different positions on the film. The measured residual resistivity ratio of the Ir films is 2
for substrate temperatures of 300C and- 8 for 630C.
142
NEW PATENTS
METAL AND ALLOYS
High Purity Hard Platinum Material
ISHIFUKU KINZOKU KOGYO K.K.
Japanese Appl. 71310,132

High purity hard Pt material with at least 99.9% purity
is obtained by adding 0.014.1 wt.% of Nb, Eu and
Er, and one or more of Be, Ca, B and Si, to Pt of high
purity. This Pt material is used for making jewellery,
such as M g s , necklaces and tie-pins.
CHEMICAL COMPOUNDS
Tris(acety1aeetonate)iridium (III)
TANAKA KMINZOKU KOGYO K.K.
In the preparation of ms(acety1acetonate)iridium

(l), Ir(II1) chloride is dissolved in H,O and reacted
with acetylacetone to give a reactant solution. The
solution is controlled so as to be alkaline, and reacted,
extracted by benzene, condensed, washed and dried.
The preparation takes place in one step, under stable
conditions at 100C and with high yield.
ELECTROCHEMISTRY
Electrolytic Reduction of Disulphide
PERMELEC ELECTRODE LTD.
British Appl. 2,291,887A

The electrolytic reduction of disuiphide in the cathode chamber of a bath partitioned by a diaphragm
uses a metallic cathode composed of Ti, Ta or Zr as
an electrode-active surface or an alloy of two or more
of Pd, Ti, Ta, Nb, Zr, Ag, etc., and a corrosion-resistant anode composed of Ti, Ta, Nb or Zr or their alloy,
coated with Ir oxide as the active material. In an example, the Ti or Zr anode is coated with _> 20 wt.% Ir
oxide. Cystine can be reduced to cysteine with high
efficiency over long periods.
Electrode Manufacture
An electrode is made by repeating a series of the following processes at least once: applying a catalyst coating solution containing SiOzsol and Pt group metal
compounds on a corrosionresistantvalve metal matrix,
drying and tiring the dried coating. The electrode is
used for electrolysis, as an insoluble electrode.
TOY0 KOHAN CO. LTD.
Platinum-Tantalum Electrodes
Japanese Appl. 7/313,980
An electrode comprises a conductivesubstrate coated
with 85-97 mole % Pt and 3-15 mole % Ta and is
used both as an anode and a cathode. After coating
the substrate with Pt and Ta components, it is heated
in an acidic atmosphere. The electrode, which is
used to ionise HzO, has a longer life, even when
the polarity of the electrodes is frequently changed.
TDK C O W .
Platinum Me& Rev., 1996, 40, (3), 143-148
Retention of Drinking Water Quality

The quality of drinking HzOis retained by electrolysis using insoluble electrodes coated with Pt, Ir oxide
and Ta oxide containing 1-50 mole% of Pt, 40-80
mole% of Ir and 10-50 mole% of Ta. The polarity
of the electrodes is changed to prevent scale adsorption on the equipment. The electrodes have longer
life, even with the changing polarity.
TDK C O W .
Electrode for Oxygen Generation

FURUKAWA ELECTRIC CO. LTD.

The structure of an electrode for 0, generation has
a base of Ti or a T i alloy, upon which is a Ti single
layer and an intermediate mixed oxide layer, comprising non-Pt metal oxides, and a mixed oxide catalytic layer mainly of a Pt group metal oxide. The electrode is used in electroplating, electrolytic refining,
electrolyticorganic synthesis and cathodic protection.
ELECTRODEPOSITIONAND
SURFACE COATINGS
Aqueous Ammoniacal Bath
w.C. HERAEUsG.m.b.H. European Appl. 693,579A
An aqueous ammoniacalbath for the electrolytic depo-
sition of Pd-Ag alloys contains: 5-50 gll Pd as a Pd

ammine complex, 2 4 0 g/l Ag as an Ag compound,
30-150 gll conductive salt, 5-100 gll aliphatic
polyamines with 2-10 amino groups and 2-50 pfl mercaptoalkane carboxylic and/or sulphonic acid and/or
salts thereof, adjusted to pH 7.0-10.0 withNH40H.
The bath is used for electroplating small components,
smps and wires with Pd-Ag alloys in the form of shiny,
ductile, non-porous and crack-free coatings.
Noble Metal Coated Metal Powder Substrates

M. J. OSTOLSKI
US.Patent 5,476,688
Noble metal is coated onto a substrate of Cu, Ni, Al,
Ti, Zr, etc., or a mixture of one of these seeded with
a second, by using a starter plating solution of ionic
Pt,Pd, Rh, Ir, Os, Ru,Au or Ag to obtain a coating
weight of 2-60 wt.% of the wholly coated product. The
substrate is immersed into one bath at 20-100C until
the bath is depleted of noble metal ion before transferring to another bath. The coatings are uniform,with
good corrosion resistance and electrical conductivity.
Electromagnetic Wave Shield Coating

KOREA MACHINERY RES. INST. Korean Appl. 9414,054
An electromagnetic wave shield coating for a plastic
surface is made by mixing a solution of 0.5-100 gll
Pd chloride and 0.5400 gA Sn chloride with acetone,
tetrahydrofuran, methylethyl ketone, etc., as the solvent. The solution is coated onto the resin surface and
then dipped into an electroless plating liquid.
143
APPARATUS AND TECHNIQUE
Diesel Engines Exhaust Gas Catalyst

European Appl. 694,332A
A catalyst for treating exhaust gas from diesel engines
comprises a Pt group metal on a ceramic support
which is a mixture of TiO,, SO,, AlzO,and ZrO,.
The
catalyst is prepared by impregnatingthe support with
a solution of the compounds of the Pt group metal,
followed by calcination. The catalyst has enhanced
CO oxidation, NOx reduction and reduced SOzoxidation and is more resistant to high temperatures.
JOHNSON MATTHEY P.L.C.
Platinum Container
TANAKA KIKINZOKU KOGYO K.K.
Japanese Appl. 81 1,O 17

A Pt container, for scientific use and manufacturing
processes, has good mechanical strength, softens less
under heating, and can prevent crystals growing. The
container is composed of a deposited layer produced
by electroforming. The Pt containers have good heat
resistance and a long service life.
Water-Tight Plug Seal Composition

SHINETSU CHEM. CO. LTD. German Appl.
1195128,232
A water-tight plug seal composition, with short moulding time, contains organopolysiloxane,organohydrogenpolysiloxane,finely-divided SiO, filler, a catalytic
amount of a Pt catalyst, and sulphide and triazine peroxide compounds. The composition is easily fixed
to the plug housing to reduce the resistance to plugging in and maintains HzO tightness. The seal has
excellent resistance to heat, cold and oil.
Exhaust Gas PurificationCatalyst

MITSUBISHI JUKOGYO K.K. European Appl. 696,470A
A catalyst for cleaning exhaust gases comprises a first
catalyst layer of Pt, Rh and/or Pd on a support and
a layer of Ir catalyst overlaying the first layer. The carrier for carrying the Ir in the second layer is a crystalline silicate, containingpreferably Al,O,, SO,, ZrO,,
TiO,, or a zeolite. The catalyst operates at high temperatures, is durable and stable. Deterioration of the
catalyst by heat, H,O and excess 0, is alleviated.
Attrition-ResistantCatalyst
World Appl. 961612A
HETEROGENEOUS CATALYSIS
ENGELHARD COW.
Palladium and Silver Containing Catalyst
especially in fluid catalytic cracking, comprisesPt supported on transition AlzO,particles which have been
impregnated with 3-8 wt.% CeO, and 2 wt.% La,O,,
followed by calcination at 2 1OOO"C, prior to Pt addition. Also claimed are: microspheresof the above bodies; and CO catalysts for use in a fluid catalytic cracking process. The attrition-resistant catalyst has high
catalytic activity, long durability and better retention in a cracking unit.

The preparation of a Pd and Ag-containing catalyst
involves contacting a solid composition of Pd, Ag and
an inorganic support material with a liquid composition comprising at least one reducing agent at I6OOC.
The contacting conditions are effective at enhancing the selectivity of the solid composition to C,H,,
when it is used as a catalyst for hydrogenating C,H,
to produce C,H,, which is also claimed. The catalyst has good activity.
PHILUPS PETROLEUM c o .
Dehydrocyclisationin Naphtha Reforming

EXXON RES. & ENG. CO.
A catalyst composition comprises a halogen and catalytically active amounts of Zn, and non-alloyed Pt,
Pd, Ir, Os, Rh, Re and/or Ru, preferably Pt, on an
A1203support. No Co or Ni is present. The catalyst
is used during naphtha reforming, giving enhanced
5+C selectivity and dehydrocyclisationof at least part
of the naphtha feed stream on contact with the above
catalyst. The catalyst is stable and suppresses undesirable hydrogenolysis reactions, thus increasing the
product yield and minimising undesirable light gas.
Hzyields are increased.
Purification of Engine Exhaust Gas

CATALER IND.CO. LTD
The purification of CO, hydrocarbons and NOx at
the stoichiometric point or in exhaust gases in 0,-rich
atmospheres involves contacting with a catalyst comprising: a porous support on which is a Pt group metal
selected from Pt, Pd and/or Rh,and one NOx adsorbent loaded on the support and selected from alkali
metals, alkaline earth metals, etc., and of average particle diameter 0.1-20 pn.The catalyst provides good
performance and high temperature durability.
An attrition-resistant catalyst as CO promoter, used
Dehydrogenationof Hydrocarbons
AMOCO cow.
World Appl. 9611,239A

The dehydrogenationof a hydrocarbon feedstockand
production of an olefinic product involves contacting
the feedstock under dehydrogenation conditionswith
0.01-5 wt.% of a Pt group metal and 0.02-10 wt.%
Zn catalyst supported on a borosilicate molecular sieve
and an alkali metal. The catalyst provides higher performance without the need for regeneration. It has an
extended operating cycle life with or without the addition of H, and increases paraffin conversion, olefin
selectivity and olefin yield. The olefinic products
are used especially as oxygenates for gasoline blending and for chemical industry feedstocks.
Catalyst for Production of p-Xylene

CHEVRON CHEM. CO.
World Appl. 9613,209A
A catalyst for the production of p-xylene from
paraflins or olefins by reforming or aromatisationcomprises an intermediate pore size molecular sieve support, Pt and one of Ga, Zn, In, Fe, Sn or B. T h e
catalyst has an activity sufficient to produce a yield of
2 30% of benzene-toluene-xylene-ethylbenzene from
a 5-9C paraffinic or olefinic feedstock. 8C aromatics
are obtained, which are enriched to above equilibrium levels in pxylene. The shape selective catalyst
produces high yields of xylenes rich in pxylene from
feed, which does not contain aromatics.
144
2~-Dichl0~hexatlu0mprope
Hydrogenolysis
Production of 2-Phenylbenzotriazolee
E.I. DU PONT DE NEMOURS & CO.
KYODO YAK=
U S . Patent 5,481,051
Monohydrogenolysis of 2,2-dichlorohexafluoropropane (1) to 2-chloro-2-hydrohexafluoropropane
(2) is effected by reacting with N, at 5 150C in the
presence of PdCr,O, catalyst, and HCl or H F acid
or mixtures of these, to give (2) with a selectivity of
> 70% based on the amount of (1) converted. (2) is
a valuable intermediate for the synthesis of other Fcontaining materials, such as CF3CHFCF,, which is
useful as a fire extinguishingagent.
Catalytic Reforming Process

U S . Patent 5,482,615
A catalytic reforming process with enhanced 5C+
selectivity, including dehydrocyclisationof at least a
portion of a naphtha feedstream comprises: contacting the feedswam with the catalpt compositionwhich
consists of a halogen and a catalytically active amount
of non-alloyed Pt and Zn on an A 2 0 3 support in the
absence of Co and Ni. The catalyst suppressesundesirable hydrogenolysis reactions, and therefore
decreases the yield of undesirable light gas made during dehydrocyclisationof the feedstream.
EXXON RES. & ENG. CO.
Controlled DecompositionProcess
o m cow.
US. Patent 5,485,722
A controlled decompositionprocess for a liquid monopropellant composition, containing hydroxylammonium nitrate, involves contacting the liquid with a
solid catalyst of Pt andor transition metal groups,
thus producing a gaseous propellant of steam, CO,
and N,. The decompositionprocess is used for wastes,
which contain hydroxylammonium nitrate, and provides a method for the continuous production of
gaseous propellant. The waste treatment and decomposition processes produce innocuous and environmentally acceptable gaseous products.
Catalyst Composition
co.
U S . Patent 5,489,565
A catalyst composition, for the selective hydrogenation of 4-1OC diolefins to their corresponding
monoolehs, contains 0.01-2 wt.% Pd andor its oxide;
0.02-10 wt.% Ag andor its oxide; 0.05-10 wt.% alkali
metal fluoride; and an inorganic support comprising Alz03,SiO,, TiO,, ZrO,, etc. It is prepared by contacting a starting material containing Pd, Ag and support material with an alkali metal fluoride solution,
then drying and calcining at 300-600C for 0.2-20
h. The catalyst is stable and can be regenerated.
PHILWS PETROLEUM
Catalyst for Exhaust Gas Cleaning

A catalyst is supported on a composite oxide carrier
comprising SO,, TiO, and CeO,. At least 1 wt.% of
Pd or P a t is dispersed and carried in the carrier.
The catalyst has improved resistance to steam and
S. It is used for cleaning exhaust gas which contains
a combustible malodorous or poisonous component,
for example, hydrocarbon and CO from engines
and industrial facilities.
BABCOCK-HITACHI K.K.
Platinum Met& Rev., 1996,40, (3)
K.K.
2-Phenylbenzotriazoles (1) are produced by the catalytic hydrogenation of azo compounds in the presence of a 0.1-10 wt.% Pt catalyst, preferably supported on active C, and inorganic bases in amounts
of 2 0.3 times mole per azo compounds in organic
solvents. Azo compounds are prepared by diazodsing
o-nitroanilines with nitrous acid and HCl and coupling the diazonium salts formed with phenols. (1)
are used as UV absorbers for polymeric coatings, etc.
Exhaust Gas Purification Catalyst

Silicate slurry containing metal, such as Pt, is coated
repeatedly onto a monolith support by a wash coat
method to form a purification catalyst for NOx, where
the slurry viscosity is controlled by adding H,O. The
apparatus used is also claimed. The purification catalyst has uniform loading of the active component.
MATSUDA K.K.
Promotion of Oil Combustion

Ceramics used to promote combustion of oil and to
reduce combustion exhaust are produced by mixing
natural zeolite powder, Pt, Au, Cu, Ca and ALO,powder and moulding the mixture into a spherical shape,
followed by firing at 750C for 6 h, and further heating at 880C for 12 h. The ceramicsreduce CO,, NOx
and unburnt HC in the exhaust. The amount of 0,
needed for combustion can be reduced by 20%.
K. SAT0
NOx Purification Catalyst

TOYOTA CHUO KENKYUSHO K.K.

A catalyst for purlfylng NOx consists of at least one
alkali metal and Pt on a porous support with the mole
ratio of the supported alkali meta1:Pt of 20-100: 1.
With t h i s catalyst, NOx emissions from automotive
internal combustion engines can be reduced over a
wide range of temperatures in excess 0,
atmospheres.
Catalysts for NH, Decomposition

NPPON SHOKUBAI co. LTD. Japanese Appl. 71289,897
A catalyst for decomposing NH, comprises at least
one binary or ternary compound oxide@) selected
ffom Ti and Si, binary compound oxides containing
Ti and Zr, and ternary compound oxides of Ti, Si and
Zr; a catalyticcomponent of an oxide of V, W and Mo,
and at least one of Pt, Pd, Rh, Ru and Ir. The catalyst is used for oxidising and decomposing NH,emitted fkom coke ovens, etc., to N, and H20.
Catalysts for Purifying Exhaust Gases

co. LTD. Japanese Appl. 71289,904
NISSAN MOTOR
Catalysts for punfying exhaust gases are multi-component compound oxides of form*.
PdJvioJWYdO,
where a = 0.01-5 wt.%; b, c and d = atomic ratio of
each element; and when b = 10, c = 0.1-1 1 and d =
30-200, and g = number of 0 atoms required. The
catalysts are effective over a wide temperature range
and are durable. They can efficiently remove NOx
from atmospheres containing excess 0,.
145
Exhaust Gas Purification
Catalyst for Ozone Decomposition

A catalyst for purifvlng exhaust gases contains Pt and
at least one metal selected from Ir and Groups IIB
and IVB elements supported on base materials.
Exhaust gas can be purified in an atmosphere with
excess 0, at low temperatures. It is used for the effective removal of CO, HC and NO, from exhaust gases.
NE CHEMCAT K.K.
Purification Catalyst for NOx
Purifying Diesel Engine Exhaust Gas

A Pd salt solution, such as Pd nitrate and Pd acetate
is supported on mordenite by immersion or ion
exchange with the coexistence of NH,ions and acetic
acid, to form a NOx purification catalyst. Pd supported on mordenite (SiO,:Al,O, ratio of 10:30) is
denatured with acidic Fe salt solution or Mg. The catalyst removes NOx efficientlyand is used in the presence of a hydrocarbon reducing agent, such as CH,.
MAN NUTZFAHRZEUGE A.G.
MATSUDA K.K.
TOKYO GAS CO. LTD.
Catalyst for Purification of Exhaust Gases

DAIHATSU MOTOR CO. LTD. Japanese & i d . 71308,578
A catalyst for exhaust gas purification, especially of
NOx, comprises a perovskite type double oxide powder, Lao,Ceo,NiO,which carries 0.04 wt.% of Rh,
and is obtained by mixing and drying a mixture of
La,&eo ,NiO, and Rh. With this catalyst, NOx can be
removed at lean range conditions.
Polymetal Multi-Gradient Reforming Catalyst

UOP
A hydrocarbonconversion catalyst comprises: a Group
VIII Pt group metal, preferably made of homogeneously dispersed Pt and a surface metal other than
Pt (preferably Pd), in a catalyticallyeffective amount;
and a non-acidic macro hole molecular sieve, such as
Lzeolite, containingan inorganicoxide binding agent.
The surface density of the metal is preferably twice
that of the centre of the catalyst. The catalyst is useful for reforming hydrocarbons for producing gasoline of high octane value. The catalyst has high catalytic activity and good stability.
Hydrogenation of Edible Fat and Oil

CHIYODA COW.
Japanese Appl. 713 16,585
A Pt catalyst is used for the hydrogenation of edible
fat and oil to obtain a product with a low content of
trans acids. Preferably, the catalyst consists of a support of specific surface area of 2 10 mlg with a porosity o f t 0.1 d g , supporting 0.1-10 wt.% of Pt catalyst(s). The method controls the formation of trans
acids and allows less severe hydrogenating conditions.
Purification of Contaminated Soil

A purification process for contaminated soil involves
heating the soil to 300-500C and evaporating any
aromatic halogens it contains by contacting with a
catalyst at 250400C in the presence of > 5% 0,.
The catalyst contains more than one of Pt, Pd, Cu,
Co, Mn, V or their oxides supported on A1,0, or
SiO,:Al,O,. The process can purify soil contaminated
by aromatic halogen without addition of any reagents.
EBARA COW.
Platinum MetaLF Rev., 1996,40, (3)
Japanese Appl. 8110,6 19

An ozone decomposition catalyst contains amorphous
Mn oxide and Pd oxide, carried on SiOz-BzO,-Al,O,
composite oxide, and also contains at least one of
Ir, Ag, La, Ce, Fe, Ni, Y and Sm. The catalyst can
decompose ozone efficiently from gases containing S
compounds and/or H,O.
German Appl. 4,424,235

A sorption-oxidation catalyst for combined sorptive
and oxidative purification of diesel engine exhaust gas
comprises a solid acid system doped with Pt metal
oxide(s) to increase barrier activity, especially after
cold start, and reduce odour emission. The catalyst
also has satisfactoryCO oxidation activity, avoids partial oxidation to odorous substances and increases the
highly volatile organic components sorption activity under load, especially after cold start.
Hydrogen Peroxide Production Catalyst

BASF A.G.
An oxidation catalyst (1) used in the preparation of
epoxide or H2OZis based on Ti or V silicates with zeolite structure and contains 0.01-20 wt.% Ru, Rh, Pd,
Os, Ir and/or Pt. The novelty is that each Pt metal is
present in t 2 different energy states. (1) is used as a
heterogeneous catalyst in the production of propylene
oxide, from olefins, H, and 0, and of H,Oz fkom H,
and 0,.It can be regenerated by controlled combustion of C deposits and reactivated, preferably with
H, or simply by washing.
CH, Steam Reforming or Oxidation Catalyst

SUED-CHEMIE A.G.
A catalyst for auto-thermal steam reforming andor
oxidising CH, reactions which proceed in parallel,
comprises Pt/Al,O, where the carrier contains 2-12
wt.% Ni and 1-10 wt.% Ce, both calculated as metal
and based on the whole catalyst. The catalysthas high
activity in both oxidation and steam reforming, and
is highly stable mechanically and catalytically at >
850C. It is used in the production of synthesis gases
or Hzfkom CI-h, for the production of MeOH, FischerTropsch hydrocarbons, 0x0 alcohols and NH,.
HOMOGENEOUS CATALYSIS
Preparation of Optically Active Cyclohex-2ene-1-one Derivatives
F. H O F F M A LA ROCHE & CO. A.G.

Optically active cyclohex-2-ene-1-one derivatives (1)
are prepared by asymmetric hydrogenation of enol
derivativesof keto-isophorone using a Rh complex of
an optically active diphosphine ligand as catalyst. The
Rh complex comprises lower alkyl or lower alkoxy,
phosphine, benzyl, etc. (1) are valuable intermediates
in the preparation of 3-hydroxy carotenoid derivatives, especially in the preparation of zeaxanthin. The
process gives high optical yields.
146
Hydrosilation Process
Anode Catalyst for Fuel Cells
US. Patent 5,481,016

A hydrosilation process using an alcohol or silylated
alcohol accelerator comprises reacting SiH and the
unsaturated reactant in the presence of a Pt catalyst,
selected from Pt compounds and Pt complexes. The
process is carried out with 0.1-10% stoichiometric
excess of SiH with respect to the unsaturated C-C
linkages in the unsaturated reactant. The concentration of Pt catalyst provides 1-1000 moles of Pt per
1 X 1O6 moles of unsaturated C-C bonds. The reaction is carried out at 15-1 7OOC. The accelerators
are effective in the presence or absence of 0 , and are
used in hydrosilation of unsaturated reactants.

STONEHART ASSOC. INC.
An anode catalyst for fuel cells contains an alloy of
1-70 at.% Ge and/or Mo and at least one of Pt, Pd
and Ru.Poisoning of the catalytic metals by CO contained in fuels is inhibited and the fuel cells can be
operated for a longer period. There is no need to purify
the fuels to remove CO.
DOW CORNING CORP.
Preparation of 2-Aryl Aliphatic Ester

U S . Patent 5,482,596
2-Aryl aliphatic ester is prepared from styrene derivatives and CO at 1 am and 25-200C in the absence
of 0, and in the presence of a catalyst composed of
a mixture of Pd(0) or Pd salts, or a mixture of Pd(O),
Pd salts and Cu salts; and phosphine or phosphine
oxide and a mixture of ligands. The reaction is used
particularlyfor preparation of the drug ibuprofen, and
the process does not require a solvent.
ALBEMARLE CORP.
4-Methylidene Cinnamic Acid Derivatives

MERCK PATENT G.m.b.H.
German Appi. 4,424,489
The preparation of substituted 4-methylidene cinnamic acid derivatives(l), with benzylidene camphor
substituents, comprises reacting an aryl halide and an
acrylic acid derivative in the presence of a Pd catalyst. The derivatives are obtained in fewer stages, with
good spaceltime yield and with little use of additives. They are UV absorbers in cosmetics.
Vinyl Carbamates
Vinyl carbamates are prepared in high yield and selectivity by reacting secondary amines and CO, with
acetylenic compounds added during reaction in the
presence of a Pt group metal compound, especially
a Ru compound. The reaction is carried out in the
presence of a tertiary amine. The process gives high
yields and/or selectivity and avoids the use of COCl,
and highly toxic organo-Hg compounds.
BASF A. G.
Phosphoric Acid Fuel Cell

FUJI ELECTRIC co. LTD.
A phosphoric acid fuel cell has an electrode catalyst
layer in which Ru powder-retained C grains are bound
together with fluororesin and laminated on a porous
C electrode base. The cell prevents a drop in cell voltage and corrosion in the C electrode base, respectively, due to the presence of CO. The cell can be
cheaply manufactured.
Hydrogen Containing Gases for Fuel Cells

H,-containing gases for fuel cells are prepared using
a selective oxidation catalyst of Pt/L-type zeolite.
The H,-containing gas is produced by reforming a
fuel to a fuel gas, then mixing with an O,-containing
gas, and also with 1 7 4 0 vol.% CO, and CO. On contact with the PtL zeolite catalyst, CO is changed to
COz.The gases obtained can be used as fuels for fuel
cells operated at low temperatures, in for example,
phosphoric acid, KOH and polymeric solid electrolyte
type fuel cells. The lifetimes of the fuel cells are
extended, due to CO being prevented from poisoning the Pt in the fuel cell electrodes.
IDEMITSU KOSAN c0. LTD.
CHEMICAL TECHNOLOGY
Preparation of 1,2-Butylene Oxide
1,2-Butylene oxide (1) is prepared by the catalytic
hydrogenation of vinyl-oxirane, using a Pd catalyst
supported on BaS04, ZrO, or TiOz, or a supported
Pd catalyst optionally containing Re. (1) is a fuel additive or a stabiliser for chlorohydrocarbons.Improved
conversion, yield and selectivity are obtained.
BASF A.G.
FUEL CELLS
ELECTRICAL AND ELECTRONIC

ENGINEERING
Supported Platinum Alloy Catalyst
Manufacture of PCB

A Pt alloy catalyst on a conductive C support contains a ternary alloy of Pt, Co and Cr as the catalytically active component. The catalyst is obtained by
co-precipitationfrom an aqueous solution of nitrates
of the alloy components onto the suspended support,
as their hydroxides; reducing the hydroxides; washing, drying and calcinating at > 800C to form an
ordered alloy. The catalyst is used for making fuel cell
electrodes. It has higher activity and stability than
other available catalysts and can be produced quickly
at lower manufacturing cost.
LEARONAL MC.
DEGUSSA A.G.

The manufacture of printed circuit boards (PCB)
involves contacting the board with an electroless Pd
solution after covering the circuit pattern with a solder mask, thereby protecting Cu from oxidation. The
contact time is sufficient to provide a finish layer of
Pd (alloy) at the required thickness, to protect the Cu
deposits in the holes and on the circuit board from
oxide formation. The finish layer is smooth and flat,
and gives good solderability. Also claimed is the
method which provides the finish layer with good wire
bonding capabilities.
147
High Density Magnetic Recording Medium

US.Patent 5,478,661
Manufacture of Polyimide Board
w m c n K.K.
A magnetic recording medium has a magnetic thin The surface of a polyimide film is treated with HNO,
film of composition Co,~o-,-b-.-y-~Ni.CrbPt.MyOl and alkali, and optionally with polyamide acid solu(where a = 0-15, b = 0-15, x = 0-20, y = 0-20, z = tion treated with PdC1, to produce polyimide board,
which has good adhesivenessto metal and good elec0110 (x,y, z # 0) and a+b+x+y+z I 60, a and b cannot both be zero; M = Si, B, Zr, Al, P, Ti, Sn andor trical characteristics. The board is heated to > 200C
In. M may be an oxide, MO,, where c = 0-5 (not zero). and a metal layer is formed by a wet plating process.
Reduction of PdCl, is achieved after further treatThe Nm is deposited by sputtering a target of MO,
incorporated into a base material of CoNiPt, CoCrPt ment. Laminated polyimide board is obtained.
or CoNiCrPt alloy. The film has a coercive squareness
of 2 0.7, a coercivity of 2 2000 Oe at a remanence of Single Crystal Fe-Si-A1 Based Alloy
3.0 x lo-emdcm and low noise. The medium is MITSUMI ELECTRIC CO. LTD.
used in high density recording.
A single crystal of an Fe-Si-Al based alloy, used for
Opto-Magnetic Recording Medium
a magnetic head, consists of: 9.35-9.55 wt.% Si,
TDK COW.
Japanese Appl. 71272,334 10-6.25 wt.% Al, 0.30-0.35 wt.% Ru; and the balThe recording medium has a multilayered structure ance Fe. The plane orientation is the (100)plane.
of layers of PtSb and MnSbPt thin films formed alter- Adding Ru to the alloy reduces rust and enhances cornately, until the specified thickness is obtained. The rosion resistance. Ru also enhances magnetic perlayers have NiAs-type crystalline structure. The total meability; starting from 47,100, a maximum magthickness of the artificial lattice film is 50-2000 A. netic permeability of 277,900was obtained at 5 M H z .
The medium records and reproduces information,
and simplifiesmagnetisationin the vertical direction. Iridium Thick Film Conductor
A.G. TECHNOLOGY co. LTD.
Spherical Bump Electrode

NIPPON STEEL cow.
Japanese Appl. 7,283,227
A spherical bump electrode for a semiconductor chip,
is made of Au alloy with 0.001-0.05 wt.% Pt and
0.0014.05wt.% In, and constituteO.OOlA3.05 wt.% of
the total composition.Componentssuch as 0.0005-0.01
w t % Pd, 0.00050.005wt.% Cu and one or more types
of 0.001A3.005wt.% Ag are also added, and also constitute O.OOl-O.O5wt.% of the total composition.
Anisotropic deformation of the electrode is prevented
and damage to the elemode during mounting is minimised. Enhanced manufacturingyield with high reliability is achieved.
Ceramic PWB Resistor
SUMlTOMO KMZOKU CERAMICS K.K.

A ceramic substrate, with a bump for mounting a chip
carrier in an external mother board, has a number
of wiring layers in and on its surface. The ceramic
substrate has a thick film electric conductor made
from W andor Mo (40-90wt.%) and Ir (60-10wt.%)
which connects the internal wiring layer and a Cu ball.
The construction provides reliable junctions which
can withstand the effect of the mounting conditions.
MEDICAL USES
Silicone-Based Dental Impression

A ceramic PWB has a thick Nm resistor layer (A) and
a conduction circuit layer (B) on a ceramic substrate.
A connection terminal layer (C) is between (A) and
(B), and a protection layer of 0.5-2 pm in thickness
is formed on (C) and is produced by baking a paste
made from Pd or Pt at 800-900C. A glass layer hides
the resistor layer. The resistor reduces the occurrence
of faults.
British Appl. 2,292,153A

Silicone-based dental impression compositionsfor the
production of crowns, inlays or dentures, comprise
100 parts by weight of organopolysiloxane(1) with
2 2 aliphatic unsaturated groupslmolecule; 0.1-30
parts of organohydrogenpolysiloxane (2)with 2 3 H
atoms directly bonded to a Si atom; 10-500 ppm, with
respect to (1) and (2) of silicone-soluble Pt compound;
5-500 parts of inorganic filler and 1-200 parts of
polyvinyl ether of 1000-50,000 degree of tpolymerisation. Compositions have good elastic properties.
Semieonductor Memory for DRAM
Dental Impression Material

A semiconductor memory for DRAM has a multilayered structure. The memory has capacitors formed
on the inner wall of contact holes. Both of the electrodes of the capacitor are formed with RuO,. The
lower electrode is made of dielectric film. There is
increased wiring connection reliabilityand the wiring
c a n be formed by a sputtering method. The value of
the capacitance and the integration density are
increased. The memory area is reduced and the manufacturing process is simplified.
MINNESOTA MINING & MFG. CO.
MATSUSlUTA ELECTRIC WORKS LTD.
NIPPON STEEL COW.
G.C.CORP.
WoruAppl. 961560A
A dental impression material which allows visual core

monitoring is claimed. It comprises a curable silicone
polymer containinga crosslinkerwith at least two S M
groups, a hydrosilation catalyst comprising a complex
of Pt and an unsaturated organo-Si material, and coreindicating dyes showing a colour change within 10
min at 25C to indicate gel point or set time.
The New Patents abstracts have been prepared from

material published by Dement Information Limited.
148

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PLATINUM METALS REVIEW

A quarterly survey of research on the platinum metals and of

Palladium Facilitates Optical Switching

Emission Control Technology

Electronic and Nuclear Magnetism in Platinum-Iron at Ultralow Temperatures

Palladium Colloid Catalyst Used in Microcontact Printing

Platinum and Biological Systems

Hydrocarbonylation in Platinum Metals Metallurgy

Single Platinum-Rhodium Gauze for Partial Oxidation

Palladium Catalysts in Organic Synthesis

Platinum Complexes Used in DNA Binding Studies

Ruthenium: A Dance to the Music of Time

Communications should be addressed to

Chiral Complexes of Platinum Metals

By Professor A. von Zelewsky

Any discussion on such specialised topics as

Platinum Metals Rev., 1996, 40, (3), 102-109

The Concept of Chirality

opposite directions, since such polarised light

Platinum Metals Rev., 1996,40, (3)

Fig. 1 The enantiomeric pair of a M(L"L),

Ingold and Prelog) is mostly used (from the

Platinum Group Metal

Fw 2 c~mputermodel repmaentationofthetwo isomersof a dinucIeareompIex, [(Ru(bpy)&Lqp~]'+

Predetermined Helical Chirality

Controlling the Chirality

Platinum Me& Rev., 1996,40, (3)

Fig. 3 Bis-bidentate ligand, where the two

the inevitable loss of at least 50 per cent of the

cule is QOW a tetradentate chelate, where two

Fq.4 Two chirally bridged bipyridine units are co-ordinated in a

Plarinum Metals Rm., 1996,40, (3)

Fig. 5 A ruthenium complex where the

a species of about 96 per cent enantiomeric

Chiral Planar Complexes

Platinum Metah Rev., 1996,40, (3)

As discussed above, octahedral complexes

Fig. 7 A selection of chiral

are intrinsically chiral. The d platinum group

Platinum Me& Rev., 1996,40, (3)

descriptors used for octahedral complexes,

Oxidative Addition Reactions

Fig. 8 A two-bladedhelix is formed by s t e r i d y demandq ligands in quare planar platinum

Platinum Met& Rev., 1996,40, (3)

1 A.Werner, Z. Anorg. Chem., 1893, 3, 267

Palladium Facilitates Optical Switching

Platinum Metals Rev., 1996, 40, ( 3 )

Emission Control Technology

Solving the Cold Start Problem

Reduction of emissions during the cold start

Platinum Metals Rev., 1996,40, (3), 110-1 11

combinations of a small close-coupled starter

Electrically Heated Catalysts

Platinum Metals Rev., 1996,40, (3)

stratified charge two-stroke engine results in

Electronic and Nuclear Magnetism in

By W. Wendler, T. Herrmannsdorfer,*S. Rehmann

Platinum Metals Rev., 1996, 40, (3), 112-1 16

magnetic moment due to the nuclear spin. Since

Strong Coupling System

Platinum Metals Rev., 1996,40, ( 3 )

Lowering the Platinum Temperature