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4588 Chem. Commun.

, 2013, 49, 4588--4590 This journal is c The Royal Society of Chemistry 2013
Cite this: Chem. Commun., 2013,
49, 4588
Bartletts discovery of noble gas fluorides, a milestone
in chemical history
Karl O. Christe*
In 1962, Neil Bartlett published a terse note in Proc. Chem. Soc. eradicating the long held dogma that
noble gases are inert and cannot form stable compounds. This historical discovery has revolutionized
our views on chemistry and has given rise to thousands of papers on noble gas chemistry. The fact that
his proposed reaction product Xe
+
[PtF
6
]

has eluded experimental detection for more than half a


century and actually was a mixture of XeF
+
and Xe
2
F
3
+
salts does not diminish the enormous impact of
his discovery. A plausible explanation for the failures to observe Xe
+
[PtF
6
]

experimentally is presented.
Attempts to prepare compounds of the noble gases date back
all the way to the 19th century.
1
Although Walther Kossel
2
in
1916 and Linus Pauling
3
in 1932 had correctly predicted that
krypton and xenon fluorides could exist, very notable experi-
mentalists including William Ramsay, Henri Moissan,
1
Andreas von Antropo,
4
Otto Ru and Walter Menzel,
5
Don
Yost and Albert Kaye
6
had failed to isolate noble gas com-
pounds. This led to the conclusion that noble gases were
indeed inert, and this statement could be found in essentially
all the chemistry textbooks prior to 1962.
Neil Bartlett did not set out to prepare noble gas com-
pounds. In 1962, while pursuing the synthesis of PtF
2
by
reduction of PtF
4
, Bartlett carried out experiments to purify
his PtF
4
starting material which was contaminated by BrF
3
. He
heated it in a stream of diluted fluorine in a Pyrex apparatus to
convert the BrF
3
to the more volatile BrF
5
. In these experiments,
he consistently obtained a red sublimate which he originally
thought
7
to be OPtF
4
but subsequently identified as O
2
+
[PtF
6
]

.
8
While this was an accidental discovery,
9
the recognition of the
significance of this result and its broader implications was a
stroke of genius, worthy of a Nobel Prize but which was never
awarded.
10,11
Bartlett reasoned that PtF
6
had to be an extraordi-
narily strong oxidizer because of its ability to oxidize O
2
to
O
2
+
[PtF
6
]

. Based on the comparable first ionization potentials


of O
2
(12.071 eV) and Xe (12.130 eV), he surmised that Xe could
also be oxidized by PtF
6
. This logic prompted him to carry out his
famous experiment
12
depicted in Fig. 1. What set Neil Bartlett
apart from the ordinary chemist was his ability to grasp the
significance of this finding. This talent, combined with excellent
laboratory skills and the courage to challenge existing dogmas,
allowed him to achieve what others had pursued for many years
in vain. The enormous impact of his discovery is best reflected by
the fact that within a year of the date of his original report already
the first of many books on noble gas chemistry was published
13
which summarized the results presented at a two-day meeting at
Argonne National Laboratory. In less than one year a large
number of noble gas compounds, including XeF
2
, XeF
4
, XeF
6
,
XeOF
4
, XeO
3
, and KrF
2
had been prepared and characterized.
Although Bartlett originally believed
12
that the product of
his Xe/PtF
6
reaction was Xe
+
[PtF
6
]

, Bartletts lifelong eorts


to isolate and identify this compound were elusive. His studies
revealed that it was mainly an XeF
+
salt of Pt
2
F
11

.
9
Does this
flaw in the interpretation of the original product diminish the
significance of Bartletts breakthrough discovery? The answer is
a clear-cut NO. Bartlett combined logical reasoning and
creative thinking while seeing problems in a broad context.
This enabled him to overcome existing dogmas and to shatter
them. It opened a whole new field of exciting chemistry.
Fig. 1 The historical Bartlett experiment, the oxidation of Xe by PtF
6
(reproduced
with permission from ref. 9).
Loker Research Institute and Department of Chemistry, University of
Southern California, Los Angeles, CA 90089, USA. E-mail: kchriste@usc.edu;
Tel: +1 213 740 3552
Received 22nd February 2013,
Accepted 25th March 2013
DOI: 10.1039/c3cc41387j
www.rsc.org/chemcomm
ChemComm
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This journal is c The Royal Society of Chemistry 2013 Chem. Commun., 2013, 49, 4588--4590 4589
The elusiveness of Xe
+
[PtF
6
]

is puzzling indeed. Its for-


mation by a one electron transfer from xenon to PtF
6
would
represent such a simple and elegant mechanism. Very recently,
a plausible explanation for the preferential formation of XeF
+
salts in the Xe/PtF
6
reaction was proposed.
14
In a paper on third
row transition metal hexafluorides it was shown by high level
quantum chemical calculations that PtF
6
can interact with F

to form an energetically favored non-classical PtF


7

anion of C
s
symmetry (Fig. 2). This anion can spontaneously lose an F atom
under formation of PtF
6

.
In classical transition metal heptafluoro anions, the nega-
tive charge is distributed relatively evenly over all the F atoms in
the cluster, resulting in structures of D
5h
, C
2v
, C
3v
symmetry
having similar energies. By contrast, in non-classical PtF
7

the
unpaired electron is localized on the external F atom which also
carries much less negative charge than the remaining fluoride
ligands. The non-classical structure is best described as an F
atom weakly complexed to PtF
6

with a long PtF bond distance


of 2.05 , comparable to 2.07 in F
2

. The main reason for the


formation of non-classical PtF
7

is the extremely high electron


anity of 164 kcal mol
1
of PtF
6
. Thus, in an F

catalyzed
system (F

is ubiquitous under the reaction conditions of


Bartletts experiment) PtF
7

can rapidly transfer an F atom to


xenon forming an XeF radical and PtF
6

. The XeF radical can


then be oxidized by a second PtF
6
molecule to give XeF
+
and
PtF
5
. The latter can react with PtF
6

forming Pt
2
F
11

. In this
manner, the only observed product is XeF
+
Pt
2
F
11

, while
Xe
+
PtF
6

is not being formed at any time. The F

anion serves
as a catalyst to lower the activation energy barrier for the
formation of a fluorine radical and its transfer to xenon. The
proposed mechanism can be summarized by the following
equations.
PtF
6
F

! PtF
7

PtF
7

Xe ! XeF

PtF
6

XeF

PtF
6
! XeF

PtF
6

PtF
6

! PtF
5
F

XeF

PtF
6

PtF
5
! XeF

Pt
2
F
11

Xe 2PtF
6
! XeF

Pt
2
F
11

Has the interest in noble gas chemistry waned since 1962


and matured during subsequent years to a point where further
discoveries have become highly unlikely? This is clearly not the
case as shown by some more recent amazing results which have
been summarized in an excellent review by Grochala covering
the progress through 2007.
15
While the original studies had
been focused on the syntheses and characterization of stable
xenon fluorides, oxofluorides and oxides and to a lesser extent
on KrF
2
,
16
in subsequent years much progress was made mainly
by Schrobilgens group in the structural characterization of
known and new species, such as FXeOXeFXeF
+
,
17
HOXeF
2
+
,
18
FXeOXeF
2
+
,
18
or XeO
2
.
19
The second area which received much attention was the
creation of novel bonds between noble gases and other elements.
These eorts have been highly successful and today noble gases
are known to form bonds with many elements of the periodic
system such as Cl, Br, I, N, C, B, S, Xe, H, Be, Sc, Ti, Cr, Mn, Fe,
Co, Ni, Cu, Ag, Au, Re, U, or Hg.
15
Although some of these bonds
are relatively weak and have been observed only in low tempera-
ture matrices
20
or supersonic jets,
21
nevertheless they are strong
enough to qualify as chemical bonds. It has also been shown that
the noble gas chemistry is not limited to xenon and krypton, but
that even argon is capable of forming compounds, such as
FArH
20
or ArAgCl.
21
Furthermore, XeF
2
and KrF
2
can act as ligands to naked metal
cations giving rise to interesting molecular structures with
coordination numbers as high as 12 in Ba(XeF
2
)
4
(AsF
6
)
2
XeF
2
.
22
Fig. 2 Classical (D
5h
, C
2v
, C
3v
) and non-classical (C
s
) structures of PtF
7

(reproduced
with permission from ref. 14).
Fig. 3 Coordination of the metal center (M = Zn and Cu) in [M(XeF
2
)
6
](SbF
6
)
2
(reproduced with permission from ref. 24).
Fig. 4 Structure of the square planar [AuXe
4
]
2+
cation in tetragonal AuXe
4
-
(Sb
2
F
11
)
2
(reproduced with permission from ref. 29c).
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4590 Chem. Commun., 2013, 49, 4588--4590 This journal is c The Royal Society of Chemistry 2013
The first metalXeF2 adduct, Ag(XeF
2
)
2
(AsF
6
),
23
was discovered
in 1991 by Bartletts group. In this compound, Ag has a
coordination number of 8 with 4 fluorine atoms originating
from XeF
2
and four from AsF
6

. Since then, many naked metal


cations have been coordinated by XeF
2
and structurally
characterized.
15
Much of this work was carried out by the group
of Boris Zemva at the Jozef Stefan Institute in Slovenia, and a
typical compound, [M(XeF
2
)
6
](SbF
6
)
2
(M = Zn and Cu),
24
is
shown in Fig. 3. It has also been shown that the coordination
of noble gas fluorides to a naked metal cation is not restricted
to XeF
2
, but can also involve XeF
4
or KrF
2
.
25,26
Perhaps the most fascinating and unexpected noble gas
compounds were Steins homoleptic cation Xe
2
+
containing
a XeXe bond,
27
and Seppelts Xe
4
+
(ref. 28) and gold com-
plexes cis-(AuXe
2
)(Sb
2
F
11
)
2
, trans-(AuXe
2
)(SbF
6
)
2
, [(AuXe)
2
F](SbF
6
)
3
,
[AuFXe
2
](Sb
2
F
11
)(SbF
6
), [(F
3
As)AuXe](Sb
2
F
11
), and (AuXe
4
)(Sb
2
F
11
)
2
(see Fig. 4) in which xenon assumes the role of a pseudo-halogen
ligand.
29
In summary, Bartletts discovery of the first noble gas
compound has not only provided a spectacular new compound
but has created a whole new field of chemistry which continues
to flourish providing us with many novel compounds at the
limits of bonding. The following excerpt from Chemical &
Engineering News best describes Bartletts achievement as
one of the most important developments in inorganic chemistry
in modern times with over five hundred noble gas compounds
having been prepared since 1962.
Notes and references
1 Attempts to prepare compounds of the noble gases date back to the
discovery of argon by Ramsay and Raleigh in 1894. Ramsay provided
Moissan in France with a sample of the gas so he could react it with
fluorine which did not succeed.
2 W. Kossel, Ann. Phys., 1916, 49, 229.
3 L. L. Pauling, J. Am. Chem. Soc., 1932, 54, 3570.
4 A. Antropo, Z. Angew. Chem., 1924, 37, 217 and 695.
5 O. Ru and W. Menzel, Z. Anorg. Allg. Chem., 1933, 213, 206; Ru
and Menzel were very experienced fluorine chemists and excellent
experimentalists but, unfortunately, pursued only the synthesis of
argon and krypton fluorides.
6 D. M. Yost and A. L. Kaye, J. Am. Chem. Soc., 1933, 55, 3890.
7 N. Bartlett and D. H. Lohmann, Proc. Chem. Soc., 1960, 14.
8 N. Bartlett and D. H. Lohmann, Proc. Chem. Soc., 1962, 115.
9 Detailed accounts of the discovery have been given by N. Bartlett,
in Fluorine Chemistry at the Millenium, Fascinated by Fluorine, ed.
R. E. Banks, Elsevier, Amsterdam, 2000, ch. 3, pp. 2955, and
N. Bartlett, The Oxidation of Oxygen and Related Chemistry, Selected
Papers of Neil Bartlett, World Scientific Series in 20th Century
Chemistry, World Scientific, Singapore, vol. 9, 1999.
10 I. Hargittai, The Road to Stockholm, Nobel Prizes, Science, and
Scientists, ch. 12, Who did not win, Oxford University Press, Oxford,
2002.
11 K. O. Christe, Nature, 2008, 455, 182.
12 N. Bartlett, Proc. Chem. Soc., 1962, 218.
13 Noble-Gas Compounds, ed. H. H. Hyman, The University of Chicago
Press, Chicago, 1963.
14 R. Craciun, D. Picone, R. T. Long, S. Li, D. A. Dixon, K. A. Peterson
and K. O. Christe, Inorg. Chem., 2010, 49, 10561070.
15 W. Grochala, Chem. Soc. Rev., 2007, 36, 16321655.
16 For a review of krypton chemistry, see J. F. Lehmann, H. P. A.
Mercier and G. J. Schrobilgen, Coord. Chem. Rev., 2002, 233234,
139.
17 M. Gerken, M. D. Moran, H. P. A. Mercier, B. E. Pointner,
G. J. Schrobilgen, B. Hoge, K. O. Christe and J. A. Boatz, J. Am.
Chem. Soc., 2009, 131, 1347413489.
18 D. Brock, H. P. A. Mercier and G. J. Schrobilgen, J. Am. Chem. Soc.,
2013, 135, DOI: 10.1021/ja312493j.
19 D. S. Brock and G. J. Schrobilgen, J. Am. Chem. Soc., 2011, 133,
62656269.
20 L. Khriachtchev, M. Pettersson, N. Runeberg, J. Lundell and
M. Raesaenen, Nature, 2000, 406, 874.
21 C. J. Evans and M. C. L. Gerry, J. Chem. Phys., 2000, 112, 1321.
22 M. Tramsek and B. Zemva, Acta Chim. Slov., 2006, 53, 105.
23 R. Hagiwara, F. Hollander, C. Maines and N. Bartlett, Eur. J. Solid
State Inorg. Chem., 1991, 28, 855866.
24 M. Tramsek and B. Zemva, J. Fluorine Chem., 2006, 127, 12751284.
25 G. Tavcar and B. Zemva, Angew. Chem., Int. Ed., 2009, 48, 14321434, have
reported the synthesis and characterization of [Mg(XeF
2
)(XeF
4
)](AsF
6
)
2
.
26 U. Breddemann, D. S. Brock, H. P. A. Mercier and G. J. Schrobilgen,
reported the synthesis and characterization of [Mg(KrF
2
)
4
]-
[AsF
6
]
2
2BrF5 in paper FLUO 19, presented at the 21st ACS Winter
Fluorine Conference, Jan. 1318, 2013, St. Pete Beach, FL, USA.
27 L. Stein, J. R. Norris, A. J. Downs and A. R. Miniham, J. Chem. Soc.,
Chem. Commun., 1978, 502504; L. Stein and W. W. Henderson,
J. Am. Chem. Soc., 1980, 102, 28562857; D. R. Brown, J. M. Clegg,
A. J. Downs, R. C. Fowler, A. R. Miniham, J. R. Norris and L. Stein,
Inorg. Chem., 1992, 31, 50415052; T. Drews and K. Seppelt, Angew.
Chem., Int. Ed. Engl., 1997, 36, 273274.
28 S. Seidel, K. Seppelt, C. van Wuellen and X. Y. Sun, Angew. Chem.,
Int. Ed., 2007, 46, 67176720.
29 (a) S. Seidel and K. Seppelt, Science, 2000, 290, 117118; (b) T. Drews,
S. Seidel and K. Seppelt, Angew. Chem., Int. Ed., 2002, 41, 454456;
(c) K. Seppelt, Z. Anorg. Allg. Chem., 2003, 629, 24272430;
(d) I.-C. Hwang, S. Seidel and K. Seppelt, Angew. Chem., Int. Ed.,
2003, 42, 43924395.
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