Art:10.2478/s11532 014 0558 7

1.
Introduction
In the last few decades considerable attention has
been paid to heterometallic clusters, including those of
platinum. There are almost one thousand two hundred
heterometallic platinum complexes for which structural
data are available. Previous reviews have classifed and
analyzed over fve hundred heterobinuclear platinum
complexes [1,2], almost four hundred heterotrinuclear
[3], over two hundred heterotetranuclear [4] and
almost ninety heteropentanuclear clusters [5]. The aim
of this review is to discuss the structural parameters
of heterohexanuclear platinum clusters, and make
comparisons with the heterobi- to heteropentanuclear
clusters.
2. Heterohexanuclear Pt clusters
There are over seventy heterohexanuclear platinum
clusters of metal compositions for which crystallographic
and structural parameters are available: Pt
5
M (x2), Pt
4
M
2

(x10), Pt
3
M
3
(x11), Pt
2
M
4
(x24), PtM
5
(x22), Pt
2
Cu
3
Fe,
Pt
2
Os
3
M (x2) and Pt
2
M
2
M
2
(x2). These parameters are
analyzed and classifed in the following sections, and
their structures are found to be complex.
2.1. Pt
5
M, Pt
4
M
2
and Pt
3
M
3
The structural parameters for the hexanuclear platinum
clusters are presented in Table 1. The structure of red
brown Pt
5
Fe [6] is seen to differ from that of black Pt
5
Re
[7]. In Pt
5
Fe [6], the metal core may be regarded as a Pt
4

Central European Journal of Chemistry
Crystallographic and structural characterization
of heterometallic platinum complexes
Part VI. Heterohexanuclear complexes
* E-mail: qmelnik@stuba.sk
Received 29 October 2013; Accepted 18 January 2014
Abstract:
Versita Sp. z o.o.
Keywords: Heterohexanuclear Platinum Structure Analyze Isomers
1
Department of Pharmaceutical Analysis and Nuclear Pharmacy,
Faculty of Pharmacy, Comenius University in Bratislava,
SK-832 32 Bratislava, Slovak Republic
2
Department of Chemistry, York University, North York, M3J 1P3 Ontario,
Canada
Milan Melnk
1
, Peter Miku
1
, Clive E. Holloway
2
Review Article
This review classifes and analyzes heterohexanuclear platinum clusters intoseven types of metal combinations:Pt
5
M, Pt
4
M
2
, Pt
3
M
3
, Pt
2
M
4
,
PtM
5
, Pt
2
M
3
M, and Pt
2
M
2
M
2
. The crystals of these clusters generally belong to six crystal classes: monoclinic, triclinic, orthorhombic,
tetragonal, trigonal and cubic. Among the wide range of stereochemistry adopted by these clusters, octahedral and capped square-
pyramidal are the most common. Although platinum is classifed as a soft metal atom, it bonds to a variety of soft, borderline and hard
metals. Nineteen different heterometal ions are involved in hexanuclear platinum clusters.The shortest Pt-M bond distance in the case
of M being a non-transition element is 2.395(4) for germanium and for M being a transition metal ion it is 2.402(2) for Cobalt. The
shortest Pt-Pt bond distance observed in these clusters is 2.532 . Several relationships between the structural parameters are identifed
and discussed.Some clusters exist in two isomeric forms and some show crystallographically independent molecules within the same
crystal. Such isomers and independent molecules are examples of distortion isomerism.
Cent. Eur. J. Chem. 12(11) 2014 1101-1126
DOI: 10.2478/s11532-014-0558-7
1101
Table 1. Crystallographic and structural data for heterohexanuclear platinum clusters (Pt
5
M, Pt
4
M
2
and Pt
3
M
3
)
a
.
COMPOUND
(colour)
Crys.cl
Sp.Grp
Z
a []
b []
c []
a [
o
]
[
o
]
g [
o
]
Chromo-
phore
M-L
[]
M-M []
M-L-M []
L-M-L
[
o
]
Ref
A: Pt
5
M
(PEt
3
)
4
(CO).
(-CO)
4
Pt
5
Fe(CO)
4
(red brown)
m
P2
1
/n
4
11.421(2)
23.653(3)
13.877(3)
95.16(2)
PtCFePt
4
PtCPFePt
2
PtC
2
PPt
3
(x2)
PtC
2
PPt
4
FeC
4
Pt
2
OC
b
1.76(4)
OC 1.97(3,6)
2.25(3,4)
Et
3
P 2.247(8,11)
2.296(8,26)
OC 1.75(3,5)
Fe 2.570(4)
2.603(4)
Pt 2.666(1)
2.895(1)
2.765
c
Fe,Pt
b
57.8(1)
118.5(1,7)
145.5(1)
Pt,Pt60.41(4,3.2)
112.0415(5,6.5)
Pt,Pt 63.2(1)
[6]
[(Pcy
3
)
4
(CO)
5
Pt
5
.
(-O)
2
(-OH)Re].
[ReO
4
].0.5Et
2
O
(black)
or
Fdd2
16
27.783(5)
55.20(1)
26.778(7)
PtOCPRePt
(x4)
PtCRePt
4
ReO
4
Pt
4
O 2.792(2)-
3.275(2))
OC not given
cy
3
P not given

O 2.792(2)-
3.275(2)
Re 2.548(2)
2.792-3.275(2)
Pt 2.747(2,35)
3.380(2)-3.714(2)
not given
not given
[7]
B. Pt
4
M
2
(NBu
4
)[{(C
6
F
5
)
2
Pt.
(-OH)(HgCl)Pt.
(C
6
F
5
)
2
}
2
(-OH)
2
].
7/4CH
2
Cl
2
(red)
(at 223(1) K)
tr
P
2
14.228(12)
17.813(12)
20.55(2)
87.03(7)
83.91(7)
83.46(5)
PtC
2
O
2
Hg
HgClPt
2
C 1.95(4,9)
HO 2.09(3,3)
Cl 2.35(1)
Hg 2.663(4,15)
2.717(4,3)
O 116(1,6)
C,C 93(2,5)
O,O 83.1(9,1.4)
O,Hg 87.8(7,7.0)
Cl,Pt 140.5(3,10.6)
Pt,Pt 78.4(1,6)
[8a]
(NBu
4
)[{(C
6
Cl
5
)
2
Pt.
(-OH)
Pt.(C
6
Cl
5
)
2
}
2
Hg
2
].CH
2
Cl
2
(garnet)
m
P2
1
/n
4
13.105(3)
29.771(6)
31.745(6)
97.63(3)
PtO
2
C
2
Hg
HgPt
2
Hg
O 2.085(8,27)
2.142(8,18)
C 1.999(12,35)
Hg 2.675(1,19)
2.943(1,42)
Pt 3.170(1,4)
O 97.2(3,27)
Hg 2.559(1)
O,O 79.0(3,2.2)
C,C 93.0(4,1.9)
172.3(5,5.9)
Hg,Pt 54.0(1,4.6)
Pt,Pt 68.5(1,60
Hg,Pt 122.6(0,1)
161.6(1,2.4)
[8b]
(PPh
3
)
4
(-CO)
4
.
Pt
4
Hg
2
(CF
3
)
2
(red)
m
P2
1
/n
4
17.845(14)
20.696(5)
20.626(4)
90.39
PtC
2
PHg
2
.
Pt
2
(x2)
PtC
2
PPt
2
(x2)
HgCPt
2
OC 2.08(2,8)
Ph
3
P 2.265(4,12)
C 2.30(2,0)
Hg 2.727(1,8)
2.775(1,22)
3.087(1,7.2)
Pt 2.7157(8)-
2.9489(9)
2.775
c
C 81.8(5,1.1)
C,P 99.6(1,9.5)
142.5(1,10.1)
Hg,Pt 56.82(2,2.5)
65.54(2,2.4)
Pt,Ot 57.32(2,30)
65.34(2,30)
Pt,Pt 55.39(2,70)
64.79(2,40)
[9]
(PPh
3
)
4
(-CO)
4
.
Pt
4
Hg
2
Br
2
(red)
m
P2
1
/c
2
20.32(3)
20.549(6)
97.932(4)
90.50(2)
PtC
2
PHg
2
.
Pt
2
(x2)
PtC
2
PPt
2
(x2)
HgBrPt
3
OC2.040(2,41)
2.160(2)
Ph
3
P 2.259(6,6)
2.274(6,3)
Br 2.515(3,8)
Hg 2.741(1,6)
2.765(1,12)
3.067(1,46)
Pt 2.725(1,3)
2.751(1,0)
3.008(1)
3.211(1)
Hg 3.617(1)
P,Hg 96.85(2,6.0)
P,Pt 144.28(2,8.4)
Pt,Pt 66.67(3,37)
Br,Pt 64.99(1)
146.32(8,6.5)
Pt,Pt 66.48(1)
[10]
(PMe
2
Ph)
4
(-CO)
4
.
Pt
4
Hg
2
I
2
(red)
m
P2
1
/m
4
10.086(2)
18.739(4)
24.764(5)
90.94(3)
PtC
2
PHg
2
.
Pt
2
(x2)
PtC
2
PPt
2
(x2)
HgIPt
3
OC not given
P not given
I 2.707(5,4)
Hg 2.732(3,16)
2.802(3,11)
3.117(3,46)
Pt 2.726(3,8)
3.011(3)
Hg 3.395(4)
P,Hg 99.5(4)
P,Pt 148.6(4)
Hg,Hg 75.6(1)
Pt,Pt 56.6(1)
75.9(1)
Hg,Pt 56.7(1,1.4)
68.2(1)
114.9(2)
not given
[11]
[{(PPh
3
)
4
Pt
2
(
3
-Se)
2
}
2
.
In
2
(-Se)
2
].
(ClO
4
)
2
.4MeOH
(brown)
m
P2
1
/c
2
14.5465(9)
27.2617(13)
18.3583(9)
106.963(1)
PtP
2
Se
2

InSe
4
Ph
3
P not given
3
Se 2.497(1,3)
2.496(1,7)
Se 2.634(1,18)
3
Se2.571(1,15)
Se 87.71(1)
Se 82.00(1)
Se,Se 81.32(1,16)
Se,Se 98.00(2)
Se,
3
Se121.14(3,2.8)
[12]
1102
M. Melnk, P. Miku, C. E. Holloway
{NBu
4
)
2
[{(C
6
Cl
5
)
4
.
(-Cl)
2
Pt
2
Ag}
2
]
(yellow)
m
P2
1
/n
4
14.528(9)
42.615(12)
19.942(10)
96.08(2)
PtC
2
Cl
2
Ag

AgPt
2
C 1.971(32,6)
2.037(26,48)
Cl 2.418(12,28)
Ag 2.751(4,4)
2.773(4,8)
Pt 3.268(3,4)
Cl 84.9(4,6)
Ag 3.87
not given
Pt,Pt 163.2(2)
[13]
[{(PPh
3
)
2
Pt(
3
-S)}
4
.
Ag
2
](BF
4
)
2
(yellow)

m
P2
1
/a
4
24.638(7)
19.722(7)
32.619(9)
94.40(4)
PtS
2
P
2
AgS
2
Ag
3
S 2.353(8,27)
Ph
3
P not given
3
S 2.389(9,10)
Ag 3.450(3)-
3.905(3)
Pt 3.314(2,36)
Ag 2.815(4)
S,S 82.6(3,1.3)
S,S 175.1(3,1.1)
[14]
[(Pcy
3
)
4
(-CO)
2
Pt
4
(-OReO
3
)
2

(red black)
trg
R3c
18
45.067(7)
26.498(2)
PtCPPt
3
(x2)
PtOCPPt
3
(x2)
ReO
4
OC 1.92(1,2)
O 2.153(9)
cy
3
P 2.298(5,30)
O 1.70(1,2)
O 1.74(1)
Pt 2.692(1)
2.761(1,36)
2.871(1)
not given
not given
[15]
[(Pmop
3
)
2
(NCS).
(
3
-NCS)Pt
2
.
(-
1
:
5
-C
5
H
4
)
2
Fe]
2
(red)
tr
P
1
15.755(8)
16.081(9)
15.287(9)
108.58(4)
107.20(4)
68.44(4)
PtCNSP
(x2)
PtCNSP
(x2)
FeC
10
1
C not given
SCN 2.04(2)
S 2.393(5)
P not given
3
SCN 2.08(2)
3
NCS 2.398(6)
not given
not given
not given
[16]
[{{(
2
-dach)Pt.
(-:
2
-betmp)}
2
.
Cu}
2
(BF
4
)](BF
4
)
3
(blue green)
tg
I4
1
/acd
4
22.498(4)
23.16(4)
Pt
II
N
2
S
2
Cu
II
O
4
not given
not given
not given
not given
[17]
C: Pt
3
M
3
[(CO)
3
Pt
3
{-Sn.
(N(SiMe
3
)
2
)
2
}
3
]
(yellow)
m
P2
1
/n
4
11.688(1)
23.582(2)
27.426(2)
94.41(1)
PtCSn
2
Pt
3
SnN
2
Pt
2
OC not given
N 2.05(2)
Sn 2.620(1,6)
Pt 2.763(1,12)
Sn,Pt 58.48(3)
Pt,Pt 60.43(2)
N,N 108(1)
Pt,Pt 63.3(/3)
[18]
(
4
-cod)Pt
3
W
3
.
(
3
-CMe)
2
(-CMe).
(CO)
6
(cp*)
3
(burgundy)
tr
P
2
11.935(6)
13.242(7)
18.193(9)
80.53(4)
81.22(4)
67.39(4)
PtC
2
W
2
PtC
2
W
2
PtC
5
W
WC
7
Pt
2
WC
8
Pt
(x2)
C 2.05(2)
3
C 2.08(2)
3
C 2.09(2,3)
4
C 2.27(2,2)
3
C 2.04(2)
OC 1.98(2,1)
5
cpC 2.35
OC 1.95(2,2)
3
C 1.91(2,8)
5
cp*C 2.33(-,1)
W 2.729(2,18)
Pt 3.109(2)
3.201(2)
W,W 148.4(1,1)
Pt,Pt 103.1(1)
Pt,Pt 70.5(1,1.4)
[19]
[{(CO)
3
Pt
3
{Fe(CO)
4
}
3
]
(dark brown)
m
P2/c
4
15.996(6)
11.843(4)
12.796(5)
92.35(3)
PtCFe
2
Pt
2
FeC
4
Pt
2
OC 1.88(2,3)
OC 1.80(2,3)
Fe 2.578(2,7)
Pt 2.589(2,3)
C,Fe 90.4(4,2)
C,Pt 149.9(4,3)
Fe,Fe 176.0(1,3.7)
Pt,Pt 60.06(2)
Fe,Pt 59.84(5,35)
119.61(5,33)
Pt,Pt 60.30(5,10)
[20]
[N(Me
3
)(CH
2
Ph)].
[(CO)
3
Pt
3
{Fe(CO)
4
}
3
]
(green)
tr
P
4
17.217(6)
10.722(4)
8.854(6)
96.25(3)
90.37(3)
93.99(4)
PtCFe
2
Pt
2
FeC
4
Pt
2
OC 1.80(3)
OC 1.76(3)
Fe 2.587(4)
Pt 2.656(1)
not given
not given
[21]
[Pt(-abz)Fe(cp)]
3
.
CHCl
3
(dark green)
m
P2
1/
/n
4
21.439/7)
11.990(7)
20.919(4)
90.79(2)
PtS
2
NC
FeC
10
S 2.31(4,6)
N 2.18(13,4)
C 2.03(27,3)
5
C not given
Fe 3.49(3)
3.67(3,2)
Pt 3.535(9)
3.691(9,7)
S,S 92(1,1)
S,N 87(2,2)
d
S,C 103(5,3)
N,C 78(8,2)
d
not given
[22]
Continued
5
M, Pt
4
M
2
and Pt
3
M
3
)
a
.
COMPOUND
(colour)
Crys.cl
Sp.Grp
Z
a []
b []
c []
a [
o
]
[
o
]
g [
o
]
Chromo-
phore
M-L
[]
M-M []
M-L-M []
L-M-L
[
o
]
Ref
1103
tetrahedron sharing its Pt(1)-Pt(5) edge with a FePt
3

lonzenge shaped moiety. The latter is created by the
triangles FePt(3)Pt(5) and Pt(1)Pt(3)Pt(5) which form
a dihedral angle of 2.1 with each other. This lozenge
is oriented in a such way that its mean plane is nearly
orthogonal to the Pt(1)Pt(2)Pt(4) plane (dihedral angle
93.3), and platinum atoms Pt(2) and Pt(4) are situated
-1.649 and 0.985 on either side of this plane. There
are eight Pt-Pt bonds (2.666(3) 2.895(1) ) and two
Pt-Fe bonds, 2.570(4) and 2.603(3) (Table 1A).
In the black Pt
5
Re cluster [7] a central RePtCO unit
with four peripheral Pt(CO)L units is found, each of which
is coplanar with and arranged like the spokes of a wheel
around the Re-Pt axis. Each peripheral PtRe unit is
bridged by a -O or -OH ligand, with the central Pt-Re
bond of 2.548(2) . The distance between the central
(PPr
i
3
)
3
Pt
3
Co
3
.
(
6
-C)(-H)(-CO)
4
.
(CO)
5
(green)
m
P2
1
/n
4
12.536(2)
24.068(4)
16.512(3)
91.72(1)
PtC
3
PCo
3
PtC
2
PCo
2
Pt
(x2)
CoC
4
Pt
3
Co
CoC
4
Pt
2
Co
CoC
4
Pt
2
.
Co
2
OC 2.09(2,7)
6
C 2.11(2,8)
P 2.262(4)
2.310(4,4)
OC 1.98(1,1)
OC 1.88(2,6)
6
C 1.86(2,3)
Co 2.599(2)
3.060(2)
2.771
c
6
C 82.6(6,3.3)
95.5(6,4.0)
165.45(8)
Pt 2.868(1)
3.260(1)
6
C 86.6(5)
101.6(5)
171.8(8)
Co 2.693(3,1)
6
C 91.7(7,5)
164.4(8)
Co,Co 57.4(1,1)
74.8(1)
87.2(1)
Co,Pt 53.9(1,3.9)
64.6(1,2.6)
78.1(1)
91.3(1)
Pt,Pt 88.7(1)
Pt,Pt 59.5(1,3)
74.2(1,1.5)
99.4(1,2.2)
Pt,Co 54.9(1,1.7)
68.0(1,2.6)
91.8(1,1.9)
[23]
Pt
3
Ir
3
(-CO)
3
.
(CO)
3
(cp*)
3
e
(dark brown)
m
P2
1
/n
8
41.811(34)
9.183(6)
21.892(14)
90.99(6)
PtC
2
Ir
2
Pt
2

IrC
8
Pt
2
PtC
2
Ir
2
Pt
2
IrC
8
Pt
2
OC 1.89(6,17)
OC 1.77(4,1)
OC 2.06(4,2)
5
cp*C not given
OC 1.90(5,15)
OC 1.79(4,1)
OC 2.07(4,6)
Ir 2.664(3,39)
C 84.0(1,7.0)
Pt 2.707(3,7)
Ir 2.670(3,31)
C 77.0(1,9.0)
Pt 2.700(3,9)
Ir,Ir 170.1(1,5.7)
Ir,Pt 59.3(1,1.1)
119.2(1,1.5)
Pt,Pt 60.0(1,2)
Pt,Pt 61.0(1,1)
Ir,Ir 175.3(1,1.4)
Ir,Pt 59.7(1,1.1)
118.4(1,1.3)
Pt,Pt 60.0(1,3)
Pt,Pt 60.8(1,1)
[24]
[{(
2
-en)Pt(-N4,N4-
bpz-N1,N1).
Pd(
2
-en)}
3
].
(NO
3
)
4
(PF
6
)
8
.5H
2
O
(yellow brown)
m
P2
1
/n
4
17.002(3)
22.827(5)
22.763(5)
93.91(3)
PtN
4
PdN
4
not given
not given
Pd 6.82(1)
Pt 7.888(1)
Pd 3.45(1,6)
9.77(1)
not given
not given
[25]
[{(
2
-en)Pt(-N4,N4-
bpz-N1,N1).
Pd(
2
-en)}
3
](NO
3
)
7
.
(PF
6
)
5
.9.75H
2
O
(yellow-brown)
(at 143(2) K)
m
P2
1
/c
4
16.920(3)
24.099(5)
22.146(4)
95.18(3)
PtN
4
PdN
4
[26]
[{(NH
3
)
2
Pt}
3
(-bpz)
3
.
{Pd(
2
-en)}
2.5
].
(ClO
4
)
6
(NO
3
)
5
.5H
2
O
(red yellow)
or
Ccca
16
31.616(6)
35.691(7)
13.355(3)
PtN
4
PdN
4
H
3
N 2.00(2,2)
bpzN 2.00(2,3)
N 2.01(2,2)
N,N 90,0
178.6(11,1.5)
N,N 80.5(7,1)
d
[27]
a. Where more than one chemically equivalent distance or angle is present, the mean value is tabulated. The frst number in parenthesis is the e.s.d., and
the second is the maximum deviation from the mean.
b. The chemical identity of the coordinated atom or ligand is specifed in these columns.
c. The mean Pt-Pt distance
d. Five-membered metallocyclic ring.
e. There are two crystallographically independent molecules.
Continued
5
M, Pt
4
M
2
and Pt
3
M
3
)
a
.
COMPOUND
(colour)
Crys.cl
Sp.Grp
Z
a []
b []
c []
a [
o
]
[
o
]
g [
o
]
Chromo-
phore
M-L
[]
M-M []
M-L-M []
L-M-L
[
o
]
Ref
1104
and peripheral platinum atoms ranges from 2.712(2)
to 2.782(2) , and between peripheral platinum atoms
from 3.380(2) to 3.714(2) . In contrast, when Re-Pt
is bridged by -O and -OH, the distance ranges from
2.792(2) to 3.275(2) , with the longest being tentatively
assigned to the -OH.
There are ten colored Pt
4
M
2
clusters, four red M = Hg
[8-11], one brown M = In [12], two yellow M = Ag [13,14],
and one each of orange M = Re [15], red M = Fe [16]
and blue green M = Cu [17] (Table 1B). The structure
of red Pt
4
Hg
2
clusters [8a] contains well separated
NBu
4
+
cations, a complex [{(C
6
F
5
)
2
Pt(-OH)(-HgCl)
Pt(C
6
F
5
)
2
}
2
(-OH)
2
]
2-
anion and CH
2
Cl
2
molecules.
The core of the complex anion is a puckered eight-
membered ring {-Pt-O(H)-}
4
to which two HgCl units are
bound, each by two Pt-Hg bonds. Each Pt centre also
has two C
6
F
5
ligands cis to each other, in such a way
that the Pt centre has a square-planar arrangement
at the base of its coordination shell. The coordination
about each Pt centre is completed by an Hg atom which
sits at the apex of a square-pyramid (mean Pt-Hg bond
length of 2.690 ).
The structure of the garnet Pt
4
Hg
2
cluster [8b] consists
of two {(C
6
Cl
5
)
2
Pt(-OH)
2
Pt(C
6
Cl
5
)
2
} moieties, connected
via a Hg
2
2+
bridge. Each mercury atom is bonded to two
platinum atoms with two different Hg-Pt bond distances
of 2.675 and 2.943 . The Hg-Hg bond distance is
2.559(1) . Each Pt atom is located approximately in the
center of the base of a square pyramid formed by two
C
6
Cl
5
and two OH groups in mutually cis positions in the
basal plane, and mercury occupying the apical position.
The mean Pt-C and Pt-O bond distances are 1.999 and
2.114 respectively. The mercury atom is located in a
distorted planar trigonal arrangement, formed by two
platinum atoms and the other mercury atom.
In another red Pt
4
Hg
2
cluster [9], four platinum atoms
form two triangles with a common Pt(1)-Pt(2) edge.
The Pt(1)-Pt(2) bond distance of 2.9489(9) is about
0.217 longer than the mean values of the remaining four
Pt-Pt bonds (2.732 ). Two {Hg(CF
3
)} units link to each
of the respective Pt
3
triangles in an asymmetrical fashion.
The remaining two red derivatives, (PAr
3
)
4
(-
CO)
4
Pt
4
Hg
2
X
2
(Ar = Ph and X = Br [10], Ar = Me
2
Ph and
X = I [11]) retain the butterfy clusters, with two wings
containing platinum atoms. Each of the mercury atoms
is bonded to the two bridging platinum atoms but to
only one of the external platinum atoms. The triangular
wings are capped asymmetrically by the Hg atoms as
shown by the Hg-Pt distances, which differ signifcantly,
varying between 2.736(1) to 3.113(1) in the former
and 2.716(3) to 3.163(3) in the latter (Table 5B).
The brown Pt
4
In
2
cluster [12] has a planar {In
2
Se
2
}
core sandwiched by two hinged {Pt
2
Se
2
} moieties. It can
also be viewed as two trigonal bipyramidal {InPt
2
Se
2
}
fragments connected at the In(III) ends by two -Se,
with a center of inversion at the centre of the structure.
The two edge-linked {Pt
2
Se
2
} butterfies (dihedral angle
129.3) are almost perpendicular (89.1) to the central
planar {In
2
Se
2
} unit, thus bestowing a C
2h
symmetry to
the molecule.
Two yellow Pt
4
Ag
2
clusters [13,14] are different
from each other. In one of them [13], the cluster
anion comprises two {Pt
2
(-Cl)
2
(C
6
Cl
5
)
4
} units double
bridging two Ag atoms, creating an eight-membered
{AgPt(Cl)
2
Pt}
2
ring in which both Pt-Pt edges are double
bridged by two chlorine atoms. The mean Pt-Ag bond
lengths are 2.762 . The homo metal distances (Pt-Pt
3.268 (average), and Ag...Ag 3.87 ) exclude any
bonding.
In the other Pt
4
Ag
2
cluster [14], the [{(PPh
3
)
2
Pt(
3
-
S)}
4
Ag
2
]
2+
cation contains two binuclear hinged
{Pt
2
S
2
(PPh
3
)
4
} moieties bridging the silver atoms via
the sulfdo ligands, creating two eight membered rings
{PtSAgS}
2
with two common SAgS edges.
The structure of the red black Pt
4
Re
2
complex [15]
contains a slightly distorted tetrahedral Pt
4
cluster with
two opposing edges, related by a crystallographic dyad
axis bridged by CO ligands. In addition, two platinum
atoms are each attached to one oxygen atom of
a terminal OReO
3
anion {Pt-O-Re, 163.8(7)}.

The structure of the red Pt
4
Fe
2
cluster [16] is shown
in Fig. 1, where it is seen that the complex has a dimeric
structure in which two NCS ligands bridge three Pt
atoms in
3
-(2S,N) fashion. The molecule lies on the
crystallographic center of symmetry.
In the blue green Pt
4
Cu
2
derivative [17] two fragments
of {(
2
-dach)Pt(betmp)} are linked by one copper(II)
atom through the carboxylate group of the betmp ligand.
In addition, a pair of [{(
2
-dach)Pt(betmp)}
2
Cu] units
form a dimer. The core of the structure has a nearly
spherical shape whose surface incorporates the six
metal centers. The line of contact between the two
monomers resembles the seam of a tennis ball. One of
the BF
4
anions is centered in the cavity resulting from
the dimerization.
There are eleven colored Pt
3
M
3
clusters with M = Sn
[18], W [19], Fe (4 examples) [20-22], Co [23], Ir [24]
and Pd (3 examples) [24-26] listed in Table 5C. In the
yellow Pt
3
Sn
3
cluster [18] each edge of the Pt
3
triangle
(average Pt-Pt bond length of 2.763 ) is capped by
Sn{N(SiMe
3
)
2
}
3
units. The mean Pt-Sn bond length is
2.620 .
The structure of the burgundy Pt
3
W
3
cluster [19] is
shown in Fig. 2. The six metal atoms in the chain are
almost coplanar, with the greatest out-of-plane deviation
(0.18 ) exhibited by Pt(1) carrying the cod ligand. The
1105
Figure 1. Structure of [(Pmop
3
)
2
(NCS)(
3
-NCS)Pt
2
(-C
5
H
4
)
2
Fe]
2
[16].
Figure 2. Structure of [Pt
3
W
3
(
3
-CMe)
2
(-CMe)(CO)
6
(cod)(cp*)
2
] [19].

1106
metal-metal bonds are also bridged by three ethylidyne
ligands. Two ethylidyne fragments [C(11)C(12) and
C(21)C(22)] adopt triple bridging modes on opposite
sides of the Pt
3
W
3
chain, while one ethylidyne group
[C(31)C(32)] edge bridges the Pt(3)-W(3) bond. The
Pt-W bond distance ranges from 2.716(2) to 2.747(2) .
The molecule of dark brown [{(CO)Pt}
3
{Fe(CO)
4
}
3
]
[20] contains a crystallographically imposed 2-fold
rotation axis that passes through the Fe(1), Pt(1), C(11)
and O(11) atoms. The six metals are arranged in a raft
structure. The Pt atoms form a central triangular cluster
(ave Pt-Pt, 2.589 ) with a Fe(CO)
4
moiety bridging
each Pt-Pt edge (ave Pt-Fe, 2.578 ). Another two
green Pt
3
Fe
3
clusters, triclinic and monoclinic [21], are
isostructural with that of dark brown Pt
3
Fe
3
[20]. The
mean Pt-Fe and Pt-Pt bond distances are 2.587(4)
and 2.656(1) in the triclinic form, and 2.596(4) and
2.750(1) in the monoclinic form.
In the dark green Pt
3
Fe
3
cluster [22], three
2-(ferrocenyl)-benzothiazolinate fragments bind
platinum(II) atoms via C, N and S atoms. Each of the
S atoms binds two platinum atoms and creates a central
six-membered {PtSPtSPtS} ring. There is no metal-
metal bond present (Table 5C).
In the green Pt
3
Co
3
cluster [23], the
6
-C atom is
located inside the Pt
3
Co
3
core, with the metal atoms
occupying essentially octahedral sites, with meridional
arrangements of the Co
3
and Pt
3
groups. However, the
core is open, since one Pt...Pt separation (3.260(1) ) is
too long for direct metal-metal connectivity.
In the dark brown Pt
3
Ir
3
cluster [24], two
crystallographically independent molecules are present,
differing mostly by degree of distortion. The main feature
is a near-planar array of metal atoms, with a central-
triangle of platinum atoms (average Pt-Pt bond length
of 2.703(3) ) each edge-bridged by an iridium atom
(average Ir-Pt bond length of 2.667(3) ). The iridium
atoms are each coordinated to a
5
-cp* group and by
two CO ligands.
The remaining three Pt
3
Pd
3
clusters [25-27] are
isostructural, containing [{(L)Pt(-bpz)Pd(
2
-en)}
3
]
12+
(L
=
2
-en [25,26] or two NH
3
[27]). The six metal atoms
form the corners of a compressed distorted trigonal
antiprism (Fig. 3). While the three Pt(II) atoms form an
equilateral triangle with side lengths of 7.888(1) , the
Pd triangle is considerably larger and nearly isosceles
(8.39(1), 8.55(1), 9.77(1) ). The six Pt-Pd distances
are about 6.82(1) .
2.2 Pt
2
M
4
There are over twenty clusters of this type for which the
structural parameters are summarized in Table 2. There
are three colorless Pt
2
Li
4
[28,29,30] clusters which
differ from each other. An orthorhombic Pt
2
Li
4
cluster
[28] contains a six-membered metallocyclic ring {-Pt-Li-
Li-}
2
. The Pt-Li bond distances range from 2.621(11) to
2.658(11) (ave 2.640 ) and Li-Li from 2.855(14) to
2.91(2) . The Pt...Pt separation is 3.382(2) . Each of
eight methyl groups bridges between a Pt atom and two
lithium atoms. In addition, each of the lithium(I) atoms is
coordinated by the O atom of the Et
2
O ligand. In triclinic
[{(
1
-Bu
t
CC)Pt(
3
-Ph
2
PO)
3
Li
2
(H
2
O)(thf)}
2
] [29] two
independent, but similar, half-molecules per asymmetric
unit were found. Each centrosymmetric Pt
2
Li
4
molecule
is made up of two identical {Pt(CCBu
t
)(PPh
2
O)
3
}
2-

fragments, staggered by 180, which sandwich a one-
dimensional lithium string consisting of four Li(I) atoms
linked through the oxygen atoms of the phosphinite
groups. The inner lithium centers [Li(2),Li(2)] are
surrounded by four oxygen atoms from four different
PPh
2
O ligands (two from each platinum fragment), while
the peripheral lithium centers [Li(1), Li(1)] interact with
only two oxygen atoms of two different PPh
2
O ligands
(one from each Pt unit), completing their coordination
spheres with two different solvent molecules each (THF
and H
2
O). The Li(2)-Li(2) bond distance of 2.57(4)
is somewhat shorter than that of Li(1)-Li(1), 2.62(3) .
In another Pt
2
Li
4
cluster [30], the molecule is formed by
two identical {OPPh
2
{Pt(CCBu
t
)
2
}PPh
2
O} fragments
which act as bidentate ligands bridging the four Li(I)
centers pairwise through the oxygen atoms of OPPh
2

ligands. This creates two planar {Li
2
O
2
} rings of {Li(1,2)
O(1,2)} and {Li(1,2)O(1,2)}, which are rigorously
coplanar as shown in Fig.4. The central Li(2), and Li(2)
atoms are doubly bridged by two H
2
O molecules.
A study of the yellow Pt
2
Tl
4
cluster [31] reveals two
eclipsed {Pt(CCBu
t
)
4
}
2-
fragments connected by four
bridging Tl(I) atoms. A highly symmetric Pt
2
Tl
4
structure
containing an octahedron of metal atoms is noted,
with the thallium centers in the equatorial plane and
the platinum(II) atoms mutually trans. Each Tl(I) atom
interacts asymmetrically with four alkynyl ligands (
3
-
2
:(Pt):
2
(Tl,Tl)), approximately forming the square-
pyramidal geometry A
4
Tl (A = midpoint of C
) with
Tl at the apex.
A hexanuclear yellow Pt
2
Hg
4
cluster [32] is formed by
two trinuclear {Pt{CH
2
C
6
H
4
P(o-tolyl)
2
}(-O
2
CCH
3
)
2
Hg(
3
-
acac)Hg(O
2
CCH
3
)} units related to each other by
a center of symmetry, connected by one oxygen atom
of the acac
2-
bridging ligand. In each unit the fve-
coordinated Pt atom is located at the center of the base
of a distorted square pyramid, with the Hg atom in the
apical position (Pt-Hg, 2.6498(2) ).
The unit cell of the yellow Pt
2
Ag
4
cluster [33]
contains six [Pt
2
Ag
4
(CCBu
t
)
8
] molecules, two of which
are located on a two-fold axis, so that there are 1.5
1107
2
M
4
)
a
.
COMPOUND
(colour)
Crys.cl
Sp.Grp
Z
a []
b []
c []
a [
o
]
[
o
]
g [
o
]
Chromo-
phore
M-L
[]
M-M []
M-L-M []
L-M-L
[
o
]
Ref
[Li
2
Pt(
3
-CH
3
)
4
.
(Et
2
O)
2
]
(colourless)
(at 183 K)
or
Pbca
4
14.8564(5)
14.3705(6)
15.8683(6)
PtC
4
Li
3
Li
2
Opt
2
3
H
3
C
b
2.116(12)
3
H
3
C 2.458(13,23)
Et
2
O 2.046(12,5)
Li 2.621-
2.658(11)
Pt 3.372(2)
Li 2.88(1,3)
C,C
b
89.5(3,5)
Li,Li 66.7(3,2)
100.9(3,2)
Li,Li 121.7(5)
[28]
[{(
1
-Bu
t
CC)Pt.
(
3
-Ph
2
PO)
3
Li
2
.
(H
2
O)(thf)}
2
].
1.75H
2
O
(colourless)
(at 150(1) K)
tr
P
2
16.1646(13)
17.1032(10)
19.0177(12)
90.441(7)
102.621(9)
98.044(9)
PtP
3
C
LiO
4
Li
(x2)
LiO
4
Li
(x2)
P 2.304(3,14)
1
C 2.010(12)
O 1.97(2,3)
O 1.91(2,1)
H
2
O 1.94(2)
thfO 1.99(2)
Li 2.60(4,3)
O 83.3(9,1.2)
Li 2.62(3)
P,P 89.6(1,1)
P,C 175.0(3)
O,O 102.4(8,9.9)
124.9(1,1.6)
Li,Li 174.0(14)
O,O 100.7(9,11.6)
123.0(11)
[29]
[(
1
-Bu
t
CC)
2
Pt.
(-Ph
2
PO)
2
Li
2
.
(-H
2
O)(Me
2
CO)
2
]
2
.
0.5Me
2
CO
(colourless)
(at 173 K)
tr
P
2
13.858(3)
13.8587(3)
24.693(7)
83.79(3)
87.53(2)
65.02(2)
PtC
2
P
2
LiO
4
Li
2
(x2)
LiO
4
Li
(x2)
1
C 2.003(6,3)
P 2.303(2,3)
H
2
O 2.048(1,0)
O 1.963(10,6)
O 1.917(10,10)
Me
2
CO not given
Li 2.610(13)
2.848(19)
O 84.5(4,1)
not given
O,O 92.9(4,1.0)
O,O 97.9(4,1.1)
[30]
[Pt(
3
-Bu
t
CC)
4
Tl
2
]
2
(yellow)
not given PtC
4
TlC
8
3
C 2.000(16,3)
2.031(13,7)
3
C 2.886(12,34)
2.931(12,17)
Tl 3.798(1,16)
Pt 3.573
Tl 4.254(-,16)
C,C 90.0(5,1.8)
Tl,Tl 118.6(1,1)
not given
[31]
[(
2
-CP)Pt.
(-
2
-ac)
2
Hg.
(
3
-acac-C,O).
Hg(
1
-ac)]
2
.
CHCl
3
(yellow)
( at 200(2) K)
tr
P
1
10.488(1)
13.158(2)
15.821(2)
77.15(1)
75.74(1)
86.39(1)
PtO
2
CPHg
2
HgO
2
CPt
2
acO 2.071(7)
2.149(7)
2
C 2.046(12)

2
P 2.229(3)
2
acO 2.104(9)
2.426(8)
2.593(9,61
C 2.133(10,24)
Hg 2.6498(2)
C 98.5(4)
O,O 78.2(2)
C,P 83.9(3)
c
O,Hg 88.5(2,1.4)
C,Hg 94.8(4)
P,Hg 97.79(8)
O,O 88.7(3,6.7)
O,Pt 77.2(2,1)
[32]
[Pt
2
(-Bu
t
CC)
8
Ag
4
]
d
(yellow)
(at 273 K)
m
C
2
6
37.062(7)
12.022(16)
20.459(3)
107.48
PtC
4
AgC
4
PtC
4
AgC
4
C 1.970(25,8)
2.034(24,29)
C 2.38(2,15)
C 2.29(2,30)
C 1.958(21,8)
2.062(24,15)
C 2.33(2,6)
C 2.34(2,11)
Ag 3.062(2,28)
3.149(2,25)
C 93.8(1,2.4)
Ag 3.199(2,30)
Ag 3.148(2,4)
C 91.4(1,6.5)
Ag 3.273
(4,40)
Ag,Ag 62.0(1,1.1)
93.1(1,4)
Pt,Pt 86.5(1.3)
Pt,Ag 59.0(1,1.8)
Ag,Ag 90.0(1,9)
Ag,Ag 60.5(1,4.0)
91.5(1,7.6)
Pt,Pt 87.2(1)
Pt,Ag 58.5(1,2.0)
Ag,Ag 90.0(1,2.0)
[33]
[Pt
2
Ag
4
(-CCBu
t
)
8
].
(bipy)
(yellow-green)
tr
P
1
10.892(3)
11.861(3)
12.778(2)
73.86(1)
77.35(1)
87.24(1)
PtC
4
AgC
4
C 2.032(7,14)
C 2.48(-,11)
C 2.236(9,8)
Ag 3.266(-,6)
Ag 3.282(1,21)
not given
not given
[34]
[(
1
-C
6
F
5
)
2
PtAg
2
.
(
3
-
2
-CCPh)
2
.
(PPh
3
)]
2
.0.5CH
2
Cl
2
(pale yellow)
tr
P
2
15.265(3)
16.866(4)
19.759(4)
106.66(2)
86.48(2)
95.86(2)
PtC
4
( x2)
AgC
3
(x2)
AgC
2
P
(x2)
1
C 2.05013,3)
C 2.05(2)
3
C 2.042(14)
C 2.42(1,15)
3
C 2.285(11)
C 2.354(12)
3
C 2.454(13)
Ph
3
P 2.395(4)
Ag 2.888(2)
3.085(2,30)
C 85.7(5,2.2)
3
C 88.5(5,3.0)
Ag 2.959(2)
C,C 90.0(5,3.6)
Ag,Ag 84.08(4)
not given
C,P 142.1(4)
3
C,P 138.8(3)
[35]
[(
1
-C
6
F
5
)
2
PtAg
2
.
(
3
-
2
-CCBu
t
)
2
.
(Me
2
CO)
2
]
2
(pale yellow)
m
P2
1
/n
2
13.862(2)
17.294(4)
14.681(5)
101.56(2)
PtC
4
AgC
4
(x2)
AgC
2
O
2
(x2)
1
C 2.032(9,10)
3
C 2.036(9,8)
C 2.61(1,10)
3
C 2.222(9,2)
3
C 2.381(8,57)
O 2.39(1,10)
Ag 2.950(1)
3.109(1,3)
Ag 3.039(2)
N,N 90.0(3,3.7)
178.4(4,3)
not given
O,O 82.6(4)
[36]
1108
[(NH
3
)
2
(-
2
-meu).
(-
2
-mec-)Ag.
(-OH
2
)(-
2
-O
2
NO).
Ag(OH
2
)(
1
-ONO
2
)]
2
.
3H
2
O
(colourless)
tr
P
1
7.421(1)
12.784(2)
14.353(2)
108.89(2)
92.45(2)
105.22(/1)
PtN
4
(x2)
AgO
4
(x2)
AgO
4

(x2)
H
3
N 2.054(10,14)
LN 2.041(10,5)
LO 2.411(8,59)
2
NO 2.459(7)
H
2
O 2.396(13)
O
2
NO 2.540(11)
LO 2.44(1,7)
Ag2.906(1)
Ag 3.553(1)
6.898(1)
N,N 90.0(3,3.7)
178.4(4,3)
O,O 77.2(1)-
151.6(3)
O,O 87.5(4)-
133.3(3)
[37]
[(
2
-dbbpy)Pt.
(-pyc)
2
Re
2
.
(-
2
-dppm)
2
]
2
.
(CF
3
SO
3
)
8
.
2.37CH
2
Cl
2
.1.18H
2
O
(red)
(at 110(2) K)
m
P2
1
/c
2
20.218(4)
28.529(6)
20.218(4)
98.78(3)
PtN
4
ReO
2
P
2
Re
2
N 1.99(2,3)
LN 1.99(2,1)
LO 2.104(17,18)
Pt 11.97
Re 2.2839(15)
N,N 89.0(9)
O,O 80.3(7,6)
[38]
[(Cl)
2
(CO)
2
Pt
2
.
{-
1
:
10
-PPh.
(C
5
H
4
)
2
Fe
2
(cp)
2
}
2
]
(orange)
m
C2/c
8
18.826(5)
13.0717(8)
50.192(3)
99.42
PtCClPPt
FeC
10
OC 1.82(2,2)
Cl 2.310(4,4)
LP 2.334(3,10)
5
C not given
Pt 2.6267(8) C,Pt 82.8(5,9)
Cl,Pt 88.4(1,8)
P,Pt 172.5(1,2.6)
not given
[39]
[[{(cp)Fe}
2
(-
10
:
2
-
bpyv)PtMe
2
Br]
2
{-
2
-
(CH
2
)
2
C
6
H
4
}]CH
2
Cl
2
(deep red)
(at 193 K)
tr
P
2
14.469(12)
15.145(11)
21.33(2)
69.46(5)
71.15(5)
81.87(6)
PtC
3
N
2
Br
FeC
10
not given
not given
[40]
(OC)
2
Pt
2
Ru
4
(CO)
16
(purple black)
m
C2/c
4
12.542(2)
15.350(4)
15.252(3)
105.32(2)
PtCRu
3
Pt
RuC
4
Pt
2
Ru
(x2)
RuC
4
PtRu
(x2)
OC 1.827(8)
OC 1.93(1,3)
OC 1.93(1,2)
Ru 2.6456(8)
2.8160(8)
2.8730(8)
Pt 2.6656(8)
Ru 2.8480(9)
Ru,Ru 62.88(2)
109.2,170.41(2)
Ru,Pt 62.06(2,1.1)
109.55(2)
Pt,Pt 55.87(2)
Pt,Ru 55.69(2)
98.64(2)
Pt,Ru 61.54(2)
[41]
(OC)
2
Pt
2
Ru
4
(CO)
16
(purple black)
or
Pna2
1
4
17.738(3)
15.596(2)
10.357(1)
PtCRu
3
Pt
RuC
4
Pt
2
Ru
(x2)
RuC
4
Pt
2
Ru
(x2)
OC 1.80(2)
OC 1.94(3)
OC 1.94(3)
Ru 2.650(2,2)
2.822(2,9)
2.878(2,17)
Pt 2.665(1)
Ru 2.864(3,11)
Ru,Ru 63.03(6,39)
108.96(5,75)
171.38(3,29)
Ru,Pt 62.13(4,2.1)
112.60(5,2.1)
Pt,Pt 55.74(4,26)
Pt,Ru 55.55(6,7)
100.72(7,19)
Ru,Ru 61.06(4,4)
[42]
[Pt
2
Ru
4
(
5
-bpeb).
(CO)
14
].0.5C
6
H
6
(gray-brown)
tr
P
2
11.759(2)
16.678(3)
11.247(2)
92.47(2)
105.86(2)
81.67(2)
PtC
2
Ru
3
Pt
RuC
X
Pt
2
Ru
2
RuC
X
Pt
2
Ru
RuC
X
PtRu
OC not given
C not given
not given
Ru 2.6911(9)
2.717(1,4)
2.860(1,11)
Ru 2.761(1)
2.777(1)
not given
not given
[43]
(OC)
2
Pt
2
(
3
-
2
-
PhCCPh)(
4
-
2
-
PhCCPh)Ru
4
(CO)
12
(brown)
m
P2
1
/c
4
16.381(2)
10.715(2)
23.987(2)
90.21
PtC
2
Ru
4
Pt
PtC
3
Ru
3
Pt
RuC
5
Pt
2
Ru
(x2)
RuC
4
PtRu
2
RuC
5
Pt
2
OC 1.90(1)
C 2.199(9)
OC 1.90(1)
C 2.113(9,32)
OC 1.90(1)
C 2.19(1,2)
2.33(1)
Ru 2.685(1)
2.7937(9)
2.891(1,19)
Pt 2.5325(6)
Ru 2.7395(9)
2.853(1,14)
Ru 2.804(1,12)
Ru,Ru 59.07(3,8)
86.98(3,6.3)
122.2;152.35(3)
Ru,Pt 63.14(3,13)
101.15(2)
Ru,Ru 87.53(
121.41(2)
Ru,Pt 63.44(2,2.3)
Pt,Pt 52.30(2,32)
Pt,Ru 61.00(3,2.6)
93.40(2,54)
Ru,Ru 55.65(2)
83.77(3)
[44]
Continued
2
M
4
)
a
.
COMPOUND
(colour)
Crys.cl
Sp.Grp
Z
a []
b []
c []
a [
o
]
[
o
]
g [
o
]
Chromo-
phore
M-L
[]
M-M []
M-L-M []
L-M-L
[
o
]
Ref
1109
[{(
4
-cod)Pt}
2
.
Ru
4
(
3
-H)
2
.
(-CO)(CO)
10
]
(brown-red)
m
P2
1
/c
4
9.261(2)
21.362(7)
16.307(4)
101.05(2)
PtC
4
Ru
3
RuC
3
HPt
2
.
Ru
3
(x2)
(x2)
RuC
3
H
2
Pt.
Ru
3
(x2)
4
C 2.20(1,4)
2.27(1,1)
OC 1.91(1,5)
H 1.80(8,3)
OC 1.85(1,2)
OC 2.14(1,13)
H 1.82(8,9)
Ru 2.672(1)
2.713(1,1)
2.834(1,29)
Ru 2.817(1)
2.974(2,15)
3.026(1,26)
Ru 2.698(1)
Ru,Ru 61.06(3,1.4)
65.60(3,71)
Pt,Ru 57.94(3,2.6)
104.14(3,41)
117.31(3,51)
Ru,Ru 61.74(3,52)
Pt,Ru 59.64(3,14)
107.65(4)
115.46(4)
Ru,Ru 56.52(3)
64.29(3,18)
[45]
(
4
-cod(CO)Pt
2
.
Os
4
(CO)
14
(gray green)
or
Pbca
8
14.781(3)
35.83(2)
11.548(2)
PtCOs
4
PtC
4
Os
2
OsC
3
PtOs
2
(x2)
OsC
4
PtOs
2
(x2)
OC 1.87(3)
4
C 2.17(3,3)
OC 1.93(3,9)
OC 1.92(3,6)
Os 2.667(2,5)
2.669(2,2)
Os 2.671(2,3)
Os 2.797(1)
2.838(2,7)
Os,Os 63.67(4,40)
126.18(5,27)
152.8(7,6.0)
Os,Os 62.15(4)
Pt,Pt 116.11(5)
Pt,Os 58.29(4,94)
116.01(5,10)
174.59(5,16)
Os,Os 116.22(5,30)
[46]
(CO)
8
Os
2
Pt
2
.
(CO)
2
Os
2
(CO)
8
(red)
or
P2
1
cn
4
10.325(2)
15.549(3)
17.748(3)
PtCOs
3
OsC
4
Pt
2
Os
(x2)
OsC
4
PtOs
(x2)
OC not given
OC not given
C not given
Os 2.655(4,3)
2.832(4,17)
2.892(4,21)
Os 2.891(3,15)
not given
not given
[47]
(CO)Pt
2
Os
4
.
(
4
-PhCCPh).
(
3
-PhCCPh)
3
.
(CO)
7
(brown)
tr
P
2
12.530(2)
21.565(4)
11.284(2)
100.3(2)
111.89(1)
76.78(2)
PtC
2
Os
4
Pt
PtC
4
Os
2
Pt
OsC
3
Pt
2
Os
2
OsC
5
Pt
2
Os
OsC
5
PtOs
2
OsC
4
Os
2
C 2.08(2,1)
OC 1.81(2)
C 2.09(2)
3
C 2.18(2)
OC 1.86(2,6)
C 2.30(2,2)
3
C 2.15(2,19)
Os 2.755(1,6)
2.989(1,26)
Pt 2.761(1)
Os 2.605(1)
2.743(1)
2.847(1)
Os 2.682(1)
2.812(1)
3.092(1)
Os,Os 58.34(3,24)
76.42(3)
116.41(3,4.24)
Os,Pt 57.43(3,4.0)
98.03(4)
Os,Os 68.50(3)
78.50(3)
126.97(3)
Os,Pt 58.86(3,5.25)
97.92(4,2.2)
Os,Os 80.14(3)
116.80(4)
[48]
(
4
-cod)
2
Pt
2
.
Os
4
(-CO)(CO)
10
(dark brown)
m
P2
1
/c
4
8.622(2)
21.917(5)
16.767(3)
95.61(2)
PtC
4
Os
3
OsC
3
Pt
2
OsC
3
Pt
4
C 2.18(1,4)
OC 2.34(3,7)
OC 1.89(3,5)
OC 2.05(3,2)
Os 2.609(1)
2.839(1,1)
2.863(1,15)
Os 2.530(1)
2.614(1)
2.703(1)
2.833(1,2)
Os,Os 60.33(3,3.9)
Pt,Pt 123.21(4,64)
Pt,Os 59.86(3,5.5)
101.86(4,53)
118.64(4,7)
Os,Os 60.60(3,7.0)
[49,50]
(
4
-cod)
2
Pt
2
.
Os
4
(CO)
12
(dark brown)
tr
P
2
11.217(2)
17.295(3)
8.866(2)
92.88(2)
105.82(2)
104.23(2)
PtC
4
Os
3
OsC
4
Pt
2
OsC
3
Pt
4
C 2.22(2,4)
OC 1.90(3,7)
Os 2.711(1)
2.739(1,2)
2.826(1,42)
2.975(1)
Os 2.777(1,18)
2.849(1,17)
Os,Os 60.63(3,2.8)
Pt,Pt 113.23(4,3.4)
Pt,Os 59.68(3,5.3)
105.97(4,3.4)
111.41(4,46)
Os,Os 60.00(3,2.0)
[49,50]
[{(MeNH
2
)Pt(-
2
-
ampy)
12
Pd
2
(
1
-
ONO
2
)
3
(H
2
O)}
2
].
(NO
3
)
2
.3.5H
2
O
d
(dark red)
m
P2/c
4
21.722(2)
22.013(5)
23.909(4)
107.57
PtN
4
PdN
2
O
2
Pd
N not given
LN 2.02(2,2)
N 2.05(1,3)
O not given
Pt 6.949(1)
6.990(1)
Pd 2.877(2)
2.855(2)
N 89.0(6,1)
N,N 173.5(7,1.6)
N,N 76.4(5,1)
[51]
c. Five-membered metallocyclic ring.
d. There are two crystallographically independent molecules.
Continued
2
M
4
)
a
.
COMPOUND
(colour)
Crys.cl
Sp.Grp
Z
a []
b []
c []
a [
o
]
[
o
]
g [
o
]
Chromo-
phore
M-L
[]
M-M []
M-L-M []
L-M-L
[
o
]
Ref
1110
Figure 3. Structure of [{(en)Pt(-bpz)Pd(en)}
3
]
12+
[25].
Figure 4. Structure of [(BuCC)
2
Pt(
3
-Ph
2
PO)
2
Li
2
(-H
2
O)(Me
2
CO)
2
]
2
[30].

1111
independent molecules per unit, differing mostly by
degree of distortion. The six metal atoms are arranged
in a slightly irregular octahedron with the platinum
atoms mutually trans, while the silver atoms are in the
equatorial plane. Each platinum atom is bonded to
four CCBu
t
groups in a slightly distorted square-planar
environment.
The structure of [Pt
2
Ag
4
(CCBu
t
)
8
]bpy [34] is
similar to the previous example [33]. However, here
the hexanuclear cluster interacts very weakly with
the 2,2-bipyridine ligand, forming an intriguing one-
dimensional polymeric array extending along the
crystallographic b axis.
Another yellow Pt
2
Ag
4
complex [35] consists of two
identical cis-{(C
6
F
5
)
2
Pt(-CCPh)
2
Ag(1)(PPh
3
)} units
joined together by two silver atoms [Ag(2) and Ag(2a)]
through bridging CCPh groups. Therefore, there are
two different types of silver atoms, terminal and bridging
in the molecule. The skeleton of the pale yellow Pt
2
Ag
4

complex [36] is similar to that of [35].
In the colorless Pt
2
Ag
4
complex [37], the cis-
(NH
3
)
2
Pt
II
moiety binds through the N3 atom of the uracil
and the N3 atom of the cytosine ring. One silver atom
is directly coordinated to the O4 of uracil and O2 of
cytosine, leading to a Pt-Ag separation of 2.906(1) .
Pairs of binuclear Pt,Ag units are linked via aqua ligands
and bridging nitrate ions to two additional silver(I) atoms
which, in turn, complete their coordination spheres by
an aqua ligand and a monodentate nitrate each. As
a result, large 12-membered rings, consisting of four Ag
atoms, two H
2
O groups, as well as two O-N-O bridges
are formed. The Ag-Ag distances in these rings vary
between 3.553(1) and 6.898(1) .
The red Pt
2
Re
4
cluster [38] contains a cationic
{(
2
-dbbpy)
2
Pt
2
(-pyc)
4
Re
4
(-
2
-dppm)
4
}
8+
unit and
CF
3
SO
3
anions. The structure of the cation is
a molecular square consisting of alternating {(dppm)
2
Re
2
}
and {(dbbpy)Pt} units at the vertices with isonicotinate
(pyc) ligands along the edges, as seen in Fig. 5. In
each binuclear Re
2
(dppm)
2
unit, the triple ReRe bond
(2.2839(15) ) is bridged by two
2
-dppm-P,P ligands
in a syn-syn arrangement. Each of the isonicotinate
groups bind to the Pt(II) center via the N atom of the
pyridine ring and to Re(II) via two chelating O atoms
of the carboxylic group. The molecule, which resides
on a crystallographic inversion center, is considerably
distorted from ideal as clearly illustrated by various
parameters within the molecule. For example, the Pt-Pt
diagonal is 11.97 whereas the diagonal defned by the
midpoints of the two Re
2
units is 13.26 .
The structure of the orange Pt
2
Fe
4
complex [39]
consists of two square-planar {PtCl(CO){P(Ph)(C
5
H
4
)
2
}
Fe(cp)} units bonded via a direct Pt(I)-Pt(II) bond
(2.6267(8) ) unsupported by any bridging ligand. The
planes are oriented approximately perpendicular to
each other, with a dihedral angle of 65.6.
In deep red [{(cp)Fe}
2
(-bpyv)Pt(Me)
2
Br}
2
{-
(CH
2
)
2
C
6
H
4
}] [40], two Pt(IV) centers are arranged above
and below the plane of the central ortho-substituted
benzene ring. The ferrocene positions of the (bpyv)
Fe
2
ligands are arranged with the unsubstituted cp ring
directed towards the central benzene ring and opposite
the bromine ligands. All of the Fe(cp) groups are directed
towards a void created by the coordination of the central
benzene ring.
Purple black (CO)
2
Pt
2
Ru
4
(CO)
16
exists in two isomeric
forms, monoclinic [41] and orthorhombic [42] which are
isostructural, differing mostly by degree of distortion. The
molecule contains an open, but folded array of six metal
atoms. Two mutually bonded ruthenium atoms Ru(1)-
Ru(2) (2.8480(9) [41] and 2.864(3) [42], are joined
to the two mutually bonded platinum atoms, 2.6656(8)
[41] and 2.665(1) [42], which are bonded to a second
pair of mutually bonded ruthenium atoms, Ru(2)-Ru(1).
The molecule contains a crystallographically imposed
2-fold rotation axis that lies perpendicular to the Pt-Ptand
Ru(1)...Ru(1) vectors. Ru(2) and Ru(2) are bonded only
to one ruthenium atom and one platinum atom (Table 2).
The gray brown triclinic Pt
2
Ru
4
cluster [43] possesses
the raft structure in which all six metal atoms lie
approximately in one plane. Both alkyne groups are
coordinated to the same side of the cluster as triple
bridges across neighboring PtRu
2
triangles. The Pt-Ru
bond distance ranges from 2.6911(9) to 2.871(1) and
R-Ru bond distances are 2.761(1) and 2.777(1) . In the
brown monoclinic Pt
2
Ru
4
cluster [44] there are two types
of PhCCPh ligands. One serves as a bridge between
three metal atoms and the other bridges between
four metal atoms. Each Pt atom has one terminally
bonded CO group, and each Ru atom has three such
CO groups. The Pt-Pt bond distance of 2.5326(6) is
shorter than the Pt-Ru bond distances, which range from
2.685(1) to 2.893(1) , and also the Ru-Ru bond
distances, 2.816(1) (ave).
In another monoclinic Pt
2
Ru
4
cluster [45], two
Pt(
4
-cod) units are connected via three Ru atoms of
a Ru
4
(
3
-H)
2
(-CO)(CO)
10
fragment. The Pt-Ru bond
distance ranges from 2.672(1) to 2.863(1) , and the
Ru-Ru distance from 2.698(1) to 3.052(1) . In gray
green orthorhombic (
4
-cod)(CO)Pt
2
Os
4
(CO)
14
[46], the
Pt atoms differ, the Pt(CO) unit being connected with
all four Os atoms with a mean Pt-Os bond distance of
2.683 , while the Pt(
4
-cod) unit bonds to two Os atoms
with a mean Pt-Os bond distance of 2.671 . The mean
Os-Os bond distance of 2.817 is much longer than the
two previously mentioned Pt-Os bonds.
1112
Figure 5. Structure of [(dbbpy)Pt(-pyc)
2
Re
2
(-dppm)]
2
8+
[38].
Figure 6. Structure of [(CO)Pt
2
Os
4
(
4
-PhCCPh)(
3
-PhCCPh)
3
(CO)
7
] [48].

1113
The hexanuclear core of red Pt
2
Os
4
[47] consists
of two edge-sharing butterfies. The angles between
the planes are: Os(1)Pt(2)Os(4)-Pt(2)Os(4)Pt(5) 38.2,
Pt(2)Os(4)Pt(5)-Pt(2)Os(3)t(5) 48.1 and Pt(2)Os(3)
Pt(1)-Os(3)Pt(5)Os(6) 46.1. The mean Pt-Os and Os-
Os bonds are 2.793 and 2.891 , respectively.
The brown Pt
2
Os
4
cluster [48] consists of an osmium
capped Pt
2
Os
3
square pyramid. It also contains three
triple bridging diphenylacetylene ligands and one which
is quadruple bridging, as shown in Fig. 6. The Pt-Pt
bond is 2.761(1) , the Pt-Os distance ranges from
2.605(1) to 3.015(1) and Os-Os from 2.682(1) to
3.092(1) . Another two brown Pt
2
Os
4
clusters
[49,50] are structurally similar and consist of a central
tetraosmium core arranged in a tetrahedral geometry
with two Pt(cod) moieties capping triangular faces. All six
Os-Os bonds lie within the range of 2.530(1)-2.838(1)
in one cluster, and 2.785(1) 2.859(1) in the other.
The Pt-Os distances span a somewhat shorter range
in the former (2.609(1)-2.883(1) ), but a slightly wider
range in the latter (2.711(1)-2.975(1) (Table 2).
The dark green Pt
2
Pd
4
complex [51] contains two
crystallographically independent molecules differing
mostly by degree of distortion. Each [{(MeNH
2
)
2
Pt(-
ampy)
2
Pd
2
(ONO
2
)
3
(H
2
O)}
2
]
2+
cation (Fig. 7) has
a crystallographic C
2
axis which passes through the two
Pt(II) centers in one molecule (A) and is perpendicular to
the Pt-Pt vector in the other (B). Consequently, adjacent
cations are mutually perpendicular in the crystal lattice.
Each trans-{Pt(MeNH
2
)
2
} unit carries two coplanar
aminopyridonate rings that are bound to Pt through
the endocycle ring N atoms and adopt a head-to-head
orientation. The two Pd
2
units each bridge the four
deprotonated exocyclic amide nitrogen atoms to give
a
3
-
2
-coordination pattern for the ampy ligands. The
resulting {Pd
2
N
2
} rings are folded along the N-N vectors,
leading to short Pd-Pd bond distances (2.877(2) and
2.855(2) ). The Pt...Pt distances are beyond bonding
at 6.949(1) (A) and 6.990(1) (B), respectively. The
separations between the midpoints between the pairs
of oppositely placed Pd
2
units are 6.276(1) (A) and
6.270(1) (B), respectively
2.3. PtM
5
, Pt
2
M
3
M, Pt
2
M
2
M
2
, Pt
3
(Pt
1-x
Ni
x
)Au
2

and Pt
2
(Pt
2-y
Ni
y
)Au
2
There are twenty two PtM
5
clusters, including a single
Pt
2
Cu
3
Fe, two Pt
2
M
2
M
2
and two Pt
2
Os
3
M clusters,
for which structural parameters are gathered in
Table 3. Two [Pt(MCl
3
)
5
]
-3
(M = Ge [52] or Sn [53]) clusters
have a similar structure containing a trigonal bipyramid
(TB) metal core. In the former, the TB is a distorted
with equatorial Pt-Ge bonds of 2.424(3), 2.399(3) and
2.480(3) , while the apical Pt-Ge bonds are 2.410(3)
and 2.391(3) . In the latter, the TB is regular with
equatorial Pt-Sn bonds of 2.5722(10) with the mean
of the apical Pt-Sn bonds at 2.6530(7) .
The molecule of a PtFe
5
complex [54] contains an
octahedral six metal atom cluster with intrapolyhedral
carbide. The Fe-Pt distances (Table 3A) indicate
signifcant distortions of the octahedral cluster core.
The lengths of the Fe-Fe bonds vary from 2.622(2) to
2.786(2) .
Figure 7. Structure of [{(MeNH
2
)
2
Pt(-ampy)
2
Pd
2
(NO
3
)
3
(H
2
O)}
2
]
2+
[51].

1114
Table 3. Crystallographic and structural data for heterohexanuclear platinum clusters (PtM
5
, Pt
2
Cu
3
Fe, Pt
2
M
2
M
2
, and PtOs
3
M
2
)
a
.
COMPOUND
(colour)
Crys.cl
Sp.Grp
Z
a []
b []
c []
a [
o
]
[
o
]
g [
o
]
Chromo-
phore
M-L
[]
M-M []
M-L-M []
L-M-L
[
o
]
Ref
A: PtM
5

(NMe
4
)
3
[Pt(GeCl
3
)
5
]
(red)
m
P2
1
/c
4
11.300(9)
14.982(16)
25.631(28)
100.81(5)
PtGe
5
GeCl
3
Pt Cl
b
2.184(7,16)
2.227(7,17)
Ge2.395(3,4 )
2.416(3,8)
2.480(3)
Ge,Ge
b
90.2(1,2.6)
c
109.3(1,1.8)
141.5(1)
175.7(1)
Cl,Cl 97.8(4,4.2)
Cl,Pt 119.5(2,4.5)
[52]
(Ph
3
PMe)
3
[Pt.
(SnCl
3
)
5
]
(red orange)
c
R3
2
15.897(1) 82.02(1) PtSn
5
SnCl
3
Pt Cl 2.347(6,4)
2.373(5,2)
Sn 2.552(1,2)
2.5722(10)x3
Sn,Sn 90.00(3,23)
Cl,Cl 97.4(2,2.7)
Cl,Pt 120.0(1,2.3)
[53]
(PPh
3
)PtFe
5
.
(
6
-C)(-CO)
2
.
(CO)
13
m
P2
1
/m
4
9.4205(6)
16.7257(10)
12.4603(11)
108.37
PtC
2
PFe
4
FeC
4
PtFe
3
(x4)
FeC
3
Fe
4

OC 2.02(1)
6
C 2.02(1)
Ph
3
P 2.276(3)
OC 1.81(1,2)
OC 2.08(1,14)
6
C 1.92(1,1)
OC 1.80(1,2)
6
C 1.91(1)
Fe 2.650(2)
2.888(1,0)
2.910(1)
Fe 2.624(2,2)
2.658(2)
2.778(2,8)
not given
not given
[54]
[(PPh
3
)(CO)Pt.
(AuPPh
3
)
5
].
Cl..Et
2
O
(red)
(at 186 K)
m
C2/c
8
35.91(1)
29.637(7)
26.025(7)
136.26(2)
PtCPAu
5
AuPPtAu
4
AuPPtAu
3
(x2)
AuPPtAu
2
(x2)
OC 1.99(6)
Ph
3
P 2.32(1)
Ph
3
P 2.27(2,2)
Au 2.590(3)
2.659(4,17)
Au 2.811(3)-
3.176(3)
2.949
c
C,P103(1)
Au,Au 67.9(1,6.6)
124.8(1,8.1)
P,Pt 161.4(8,4)
170.9(6,1.6)
[55]
(CO)PtRu
5
(
6
-C).
(-CO)(CO)
14
(red)
m
P2
1
/n
4
9.341(2)
14.957(3)
36.80(1)
90.38(2)
PtC
3
Ru
4
RuC
5
PtRu
3
RuC
4
PtRu
3
RuC
4
PtRu
2
(x2)
RuC
4
Ru
4
PtC
3
Ru
4
RuC
5
PtRu
3
RuC
4
PtRu
3
RuC
4
PtRu
2
(x2)
RuC
4
Ru
4
OC 1.87(2)
OC 2.13(1)
6
C 2.04(1)
OC 1.91(2,10)
OC 1.99(2,1)
6
C 2.05(2,3)
OC 1.89(1)
OC 2.14(1)
6
C 2.05(1)
OC 1.90(2,4)
O 1.99(2,1)
6
C 2.05(1,3)
Ru 2.777(1)-
3.045(2)
2.911
c
6
C 90.6
(5,5.8)
Ru 2.826(2)-
2.951(2)
2.892
c

6
C 89.7
(5,3.1)
Ru 2.779(1)-
3.046(1)
2.911
c
6
C 90.4
(5,5.5)
Ru 2.824(2)-
2.965(2)
2.895
c
6
C 89.8
(5,3.3)
Ru,Ru 89.30(4,2.6)
Pt,Ru 89.73(4,1.2)
Ru,Ru 89.77(4,4.3)
Ru,Ru 89.74(4,2.0)
Pt,Ru 89.59(4,1.8)
Ru,Ru 90.18(4,3.5)
[56]
(PBu
t
3
)PtRu
5
.
(
6
-C)(-CO)
2
.
(CO)
13
(red)
tr
P
2
9.9510(5)
12.1523(6)
16.8957(8)
79.79
87.34
72.94
PtCPRu
4
RuC
X
PtRu
3

RuC
X
Ru
4
OC not given
Bu
t
3
P

not given
not given
Ru 2.7966(5)
3.1413(5)
3.1473(5,10)
Ru 2.8580
(7,5)
2.9288(7,9)
not given
not given
[57]
(
4
-cod)PtRu
5
.
(
6
-C)(-CO)
4
.
(CO)
10
d
(red orange)
tg
P4
1
2
1
2
16
17.302(4)
38.128(5)
PtC
5
Ru
4
RuC
X
PtRu
3

RuC
X
Ru
4
RuC
5
Ru
4
RuC
X
PtRu
3
RuC
X
Ru
4
4
C 2.21(3,1)
2.27(3.3)
6
C 2.04(2)
OC not given
OC not given
6
C 2.06(2)

4
C 2.22(3,2)
2.28(3,0)
6
C 2.06(2)
6
C 2.05(2)
Ru2.848(2,5)
2.962(2)
3.072(2)
Ru 2.826(3)-
2.944(3)
2.884
c
Ru2.860(2,2)
2.964(2)
3.074(2)
Ru 2.822(3)-
2.967(4)
2.883
c
Ru,Ru 59.19(8,30)
not given
Ru,Ru 59.06(7,80)
not given
[58]
1115
[(PPh
3
)PtRu
5
.
(
6
-C)(-CO).
(CO)
13
(PPh
3
)
(red)
m
P2
1
/c
4
17.4020(3)
13.7880(4)
26.6030(7)
106.77
PtCPRu
3
RuC
X
PtRu
3

RuC
X
Ru
4
6
C 2.062(2)
Ph
3
P 2.269(2)
6
C 2.071(8)
Ph
3
P 2.377(2)
Ru 2.7715(7)-
2.976(1,16)
3.0092(8)
6
C 84.94(8)
Ru 2.8247(9)-
3.0403(9)
2.903
c
/8
6
C 85.8(1,1)
96.05(8)
not given
not given
[58]
[(PPh
3
)PtRu
5
.
(
6
-C)(-CO)(CO)
14
(red)
m
P2
1
2
9.2740(3)
23.5940(8)
9.8433(2)
116.49 PtCPRu
4
RuC
X
PtRu
4
RuC
X
Ru
4

6
C 2.05(1)
Ph
3
P 2.272(2)
6
C 2.042(8)

Ru 2.7945(8)
2.937(1,36)
3.0817(7)
6
C 175.1(5)
Ru 2.814(1)-
2.948(1)
6
C 173.8(6,2.9)
not given
not given
[58]
(PMe
2
Ph)PtRu
5
..
(
6
-C)(-CO)(CO)
14
d
(red)
or
Pna2
1
?
44.897(5)
14.590(2)
10.208(2)
PtC
2
PRu
4
PtC
2
Ru
4

P 2.26(1)
P 2.27(1)
not given
not given
[59]
PtRu
5
(
6
-C).
(CO)
14
(PMe
2
Ph)
2
(red)
m
P2
1
/n
?
9.407(1)
25.955(7)
9.980(1)
113.41(1)
PtC
2
Ru
4
not given not given [59]
[(
2
-dppe)PtRu
5
.
(
6
-C)(-C
60
).
(-CO)(CO)
10
].2CS
2
(orange)
tr
P
2
12.018(1)
16.234(1)
21.260(1)
67.780(1)
74.277(1)
77.090(1)
PtP
2
CRu
4
RuC
X
PtRu
3
RuC
X
Ru
4
2
P not given
6
C 2.039(6)
6
C 1.981(6)
2.071(6,36)
2.169(6)
Ru 2.8745(6)
2.961(-,25)
3.1478(6)
Ru 2.8149(7)-
3.0465(7)
2.885
c
not given
not given
[60]
(
2
-dppe)PtRu
5
(
6
-C).
(-CO)
2
(CO)
12
(red)
m
P2
1
/n
4
14.596(1)
19.693(1)
15.693(1)
99.43
PtP
2
CRu
4
RuC
X
PtRu
3
RuC
X
Ru
4
2
P not given
6
C 2.054(8)
6
C 2.028(8,10)
2.075(8,18)
2.102(8)
Ru 2.924(-,29)
3.062(-,59)
Ru 2.793(1)-
2.949(1)
2.869
c
not given
not given
[60]
(PBu
t
3
)PtRu
5
(
5
-C).
(-CO)
2
(CO)
13
d
(red)
(at 190 K)
m
P2
1
/n
4
12.4684(10)
17.9669(15)
17.3482(14)
102.613(2)
PtC
2
PRu
2
RuC
X
PtRu
3
PtC
2
PRu
2
RuC
X
PtRu
3
OC not given
P not given
not given
not given
not given
Ru 2.7894(5)
2.8018(5)
3.3076(5)
Ru 2.860(-,33)
Ru 2.8213(5)
2.8282(5)
3.1603(5)
Ru 2.860(-,33)
not given
not given
not given
not given
[57]
(CO)PtRu
5
(
5
-C).
(
3
-Ph)CCPh).
(-PhCCPh)
d
(red)
m
P2
1
/n
8
19.586(5)
12.073(2)
36.467(6)
97.26(2)
PtC
4
Ru
3
RuC
3
PtRu
3
(x2)
RuC
2
PtRu
3
RuCRu
3
(x2)
PtC
4
Ru
3
RuC
3
PtRu
3
RuC
2
PtRu
3
RuCRu
3
OC not given
C 2.16(1,10)
C 2.16(1,8)
5
C 2.01(1,1)
2.09(1,3)
C 2.17(1,12)
OC not given
C 2.15(1,8)
3
C 1.98(1)
2.06(1,3)
Ru 2.741(1)
2.900(1,30)
C 78.3(4,3)
Ru 2.684(2)-
3.023(2)
2.857
c
5
,C90.3(5,7.1)
Ru 2.745(1)
2.908(1,53)
C 78.3(4,1.2)
Ru 2.673(2)-
3.090(2)
2.911
c
5
C 90.4(5,3.7)
not given
Ru,Ru90.00(4,3.6)
Pt,Ru110.64(4,1.0)
118.73(4,30)
not given
Ru,Ru 90.00(4,4.1)
Pt,Ru 111.55(4)
119.56(4,2.1)
[61]
Continued
5
, Pt
2
Cu
3
Fe, Pt
2
M
2
M
2
, and PtOs
3
M
2
)
a
.
COMPOUND
(colour)
Crys.cl
Sp.Grp
Z
a []
b []
c []
a [
o
]
[
o
]
g [
o
]
Chromo-
phore
M-L
[]
M-M []
M-L-M []
L-M-L
[
o
]
Ref
1116
(CO)PtRu
5
(
5
-C).
(
3
-EtCCEt).
(-EtCCEt).
(CI)
12
(red)
or
Pna1
1
2
19.951(3)
9.905(2)
47.180(2)
PtC
4
Ru
3
RuC
4
PtRu
3
(x3)
RuC
3
Ru
3
(x2)
OC 1.80(3)
C 2.15(3,5)
OC 1.90(3)
C 2.15(2,8)
5
C 1.98(2,3)
2.07(2,4)

Ru 2.720(2)
2.937(2,60) Ru
2.664(2)-
3.129(2)
2.896
c
5
C90.7(8,8.6)
Ru,Ru 53.90(5)
65.94(5,38)
Ru,Ru 61.17(7,3.5)
90.00(7,3.0)
Pt,Ru 63.92(6,1.8)
108.81(7,1.5)
119.45(7,6.2)
[62]
[N(PPh
3
)
2
][PtRh
5
.
(
3
-CO)
4
(CO)
12
]
(brown)
tr
P
2
16.596(7)
15.655(7)
10.692(6)
95.02(9)
85.35(8)
81.37(8)
PtC
3
Rh
4
RhC
3
PtRh
3
OC 1.80(2)
3
OC not given
OC 1.70(2)
3
OC not given
Rh 2.778(2,2)
2.802(2,9)
Rh 2.698(2)
2.827(2)
2.760
c
not given
not given
[63]
[(PPh
3
)PtOs
5
.
(
4
-S)(-CO).
(CO)
14
(dark brown)
m
P2
1
/c
4
8.986(7)
16.605(5)
26.005(8)
97.62(4)
PtCPOs
3
OsC
3
SPtOs
4
(x3)
OsC
3
SOs
4
(x2)
C 1.82(4)
Ph
3
P 2.311(4)
OC 1.88(2,10)
OC 2.08(2,5)
4
S 2.469(4,40)
Os 2.646(1)
2.791(1)
2.986(1)
Os 2.703(1)-
2.919(1)
2.840
c
S 69.6(1,3.4)
107.5(1,5)
C 80.9(5)
C,P 89.6(7)
Os,Os 61.20(2.2.6)

Os,Os 60.78(2,1.9)
89.37&(2,1.6)
141.5(4)
Pt,Os 59.40(2,4.8)
120.4(6,3.6)
[64]
[(PPh
3
)PtOs
5
.
(
3
-S)(CO)
15
.
(PPh
3
)].
0.25CH
2
Cl
2
(purple)
tr
P
2
12.538(2)
15.958(2)
18.061(2)
63.00(1)
76.63(1)
65.68(1)
PtCSPOs
3
OsC
3
SPtOs
2
OsC
3
POs
4
OC 1.88(2)
4
S 2.333(4)
Ph
3
P 2.362(5)
OC 1.87(2,11)
4
S 2.443(4)
2.535(5,15)

Ph
3
P 2.371(5)
Os 2.762(1)
2.818(1)
3.030(1)
Os 2.719(1)-
2.984(1)
2.848
c
S,Os 56.3(1,2.2)
84.0(1)
Os,Os 60.93(3,1.6)
90.78(3)
Os,Os 60.0(3,5.0)
116.85(4,4.5)
148.68(4)
Pt,Os 58.18(3,6.8)
87.70(3,5)
131.31(4)
[64,65]
(OC)PtOs
5
.
(-H)
4
(CO)
17
(red)
m
P2
1
2
8.875(5)
19.47(1)
9.370(3)
116.42(3)
PtCOs
5
OsC
3
PtOs
4
OC 1.87(5)
Os 1.89(7,17)
Os 2.762(3)-
3.052(3)
2.870
c
/5
Os 2.769(3)-
2.950(3)
2.887
c
/4
Os,Os 61.09(8,2.8)
117.2(1,6.9 )
172.5(1,2.2)
Os,Os 60.00(7,3.3)
Pt,Os 59.50(7,2.0)
[66]
PtOs
5
(
3
-S).
(-H)
6
(CO)
15
e
(red)
tr
P
6
19.541(6)
23.071(3)
9.771(2)
94.69(1)
100.8(2)
98.90(2)
PtSOs
5
OsC
3
SPt
OsC
3
Pt
PtSOs
5
PtSOs
5
3
S 2.38(1,1)
OC 1.95(4,1.6)
3
S 2.413(7,22)
Os 2.667(2)-
2.901(2)
2.766
c
S 74.5(2,1.0)
Os 2.890(2)-
2.950(2)
2.921
c
S 75.3(2,6)
Os 2.669(2)-
2.905(2)
2.770
c
Os 2.673(2)-
2.897(2)
2.766
c
Os,Os 64.52(5,4.2)
113.75(5,1.9)
130.64(6,7)
163.26(7,98)
O s,Os 60.00(5,5)
Pt,Os 57.81(5,1.8)
[66]
PtOs
5
(-H)
6
.(CO)
16
(red)
m
P2
1
/n
4
11.810(4)
15.656(4)
16.286(6)
109.15(3)
PtH
3
Os
5
OsC
3
H
2
PtOs
2
(x3)
OsC
3
H
2
PtOs
5
(x2)
H 1.96(-,1)
2.03

OC 1.81(3,7)
H 1.81(-,7)
2.10(-,3)
Os 2.664(2)-
2.954(3)
2.739
c
Os 2.864(1,6)
2.911(2,1)
2.887
c
Os,Os 64.24(4,3.4)
116.52(4,1.3)
147.73(5,1.3)
176.10(4)
Os,Os 60.00(4,1.2)
Pt,Os 57.89(4,6.0)
[67]
B: Pt
2
Cu
3
Fe
[Fe{-
5
:
1
-C
5
H
4
)
2.
Pt
2
(-CCPh)
6
Cu
3
]
(green)
m
P2
1
/c
4
12.151(6)
23.435(7)
16.835(5)
103.00(3)
PtC
4
Cu
2
CuC
4
Pt
FeC
10
C not given
C 2.192(11,61)
C 1.975(9,10)
5
C not given
5
C not given
Cu 2.845(5)-
2.975(5)
not given
not given
not given
[68]
Continued
5
, Pt
2
Cu
3
Fe, Pt
2
M
2
M
2
, and PtOs
3
M
2
)
a
.
COMPOUND
(colour)
Crys.cl
Sp.Grp
Z
a []
b []
c []
a [
o
]
[
o
]
g [
o
]
Chromo-
phore
M-L
[]
M-M []
M-L-M []
L-M-L
[
o
]
Ref
1117
C: Pt
2
M
2
M
2
[{Pt(-
3
-mec)
4
.
Co(H
2
O)Na}
2
].
(NO
3
)
4
.4H
2
O
(red)
tr
P
2
12.161(5)
12.364(3)
12.846(6)
117.60(3)
111.83(4)
90.87(3)
PtN
4
Co
CoN
4
Opt
NaO
6
3
N 2.012(9,26)
3
N
1.918(11,14)
H
2
O 1.975(9)
O 2.330-
2.694(9)
Co 2.402(2)
Na 3.369(5)
N,N 90.0(4,5)
176.0(4,8)
Co,N 175.33(8)
N,N 90.0(4,1.4)
O,Pt 179.0(3)
O,O 68.2-158.3(4)
[69]
Pt
2
Ru
2
W
2
(
3
-tlm)
2
.
(-CO)
2
(CO)
9
(cp)
2
(black)
or
Pbnb
8
9.246(4)
46.799(8)
11.972(5)
PtC
2
W
2
Ru
2
PtC
3
WRu
WC
7
Pt
2
Ru
2
WC
8
Pt
RuC
4
Pt
2
W
RuC
5
PtW
OC 2.12(3)
3
C 2.11(3)
OC 1.78(5)
OC 1.93(5)
3
C 2.14(3)
OC 1.96(4,12)
OC 1.95(4,6)
5
cpC not given
3
C 1.98(3,3)
OC 1.93(6,15)
OC 2.21(5)
3
C 2.16(3,5)
W2.751(3,51)
3
C 86(1)
Ru2.730(4,58)
3
C 83(1)
Pt 3.064(4)
W 2.739(3)
3
C 83(1)
Ru 2.677(3)
3
C 97(1)
Ru 2.800(5,43
3
C 84(1,2)
W,W 164.5(1)
Ru,Ru 114.3(1)
W,Ru 101.8(1)
134.7(1)
W,Ru 63.3(1)
Pt,Pt 67.6(1)
Pt,Ru 58.3(1,2.3)
72.7(1)
Pt,Pt 69.9(1)
Pt,W 60.0(1,2)
[70]
D: PtOs
3
M
2
[(Pcy
3
)PtOs
3
Sn.
(-H)
2
(Cl)(OEt
2
).
(CO)
10
(SnCl
3
)]
(orange)
m
P2
1
/n
4
18.887(8)
12.697(8)
20.475(8)
103.63(3)
PtHCPOs
2
.
Sn
OsC
3
HPt.
Os
2
Sn
OsC
2
H
2
Pt.
Sn
2
Os
OsC
4
Os
2
Sn
SnOClPt.
Os
3
H not given
OC 2.04(17)
cy
3
P 2.388(14)
OC 1.88(7,15)
H not given
Et
2
O 2.49(4)
Cl 2.37(3,3)
Os 2.782(3)
2.865(3)
Sn 2.975(5)
Sn 2.610(5,2)
2.645(5)
3.058(5)
Os3.047(3,45)
C,P 93.2(44)
P,Os 114.4(4)
163.0(4)
P,Sn 131.1(4)
Os,Os 66.4(1)
Os,Sn 53.0,64.1(1)
Pt,Os 58.1(1)
105.3(1)
Pt,Sn 58.3(1,2.8)
Sn,Os 50.9(1,8)
64.1(3)
105.4(2)
Os,Os51.7(65.2(1)
Pt,Os 58.1(1,3.2)
109.8(2)
Os,Os 65.6(1)
117.8(1)
[71]
[(
4
-cod)PtOs
3
(CO)
9
.
(
4
-cpbcp-
5
:
5
).
Fe
2
(cp)
2
]
(brown)
tr
P
2
11.359(2)
18.684(5)
10.827(2)
96.4(2)
PtC
5
Os
2
OsC
3
PtOs
2
OsC
4
PtOs
2
OsC
5
Os
FeC
10
4
C not given
3
C 2.18(1)
OC not given
C 2.18(1,2)
3
C 2.23(1,2)
5
C not given
Os 2.6974(9)
2.7817(9)
Os 2.7245(9)
2.8351(8)
not given
not given
not given
[72]
[Pt
3
(Pt
0.83
Ni
0.17
)
(AuPPh
3
)
2
(-
CO)
4
(CO)(PPh
3
)
3
].
(thf)(Pr
i
2
O)
(dark brown)
(at 173 K)
tr
P
2
13.107(1)
13.454(1)
29.459(3)
96.90(1)
100.62(1)
105.81(1)
PtC
2
P
(x3)
MC
3
Au
(Pt
0.83
Ni
0.17
)AuPM
2
(x2)
OC not given
Ph
3
P 2.232(8,7)
OC not given
OC 1.89(4)
Ph
3
P 2.282(8,4)
M 2.713(1,21)
Pt 3.286(1)
Au 2.710(1,10)
Pt 2.941(1)
Au 3.043(1)
not given
not given
not given
[73]
[Pt
3
(Pt
0.26
Ni
0,74
)
(AuPPh
3
)
2
(-
CO)
4
(CO)(PPh
3
)
3
].
(thf)(Pr
i
2
O)
(dark brown)
(at 173 K)
tr
P
2
13.117(1)
13.459(1)
29.4679(3)
96.88(1)
100.59(1)
105.88(1)
PtC
2
P
(x3)
MC
3
Au
AuPM
2
(x2)
OC not given
Ph
3
P 2.251(6,2)
OC not given
OC 1.85(3)
Ph
3
P 2.296(6,1)
M 2.708(1,17)
Pt 3.289(1)
Au 2.738(1,40)
Pt 2.949(1)
Au 3.039(1)
not given
not given
not given
[73]
[Pt
3
(Pt
1.58
Ni
0.42
)
(AuPPh
3
)
2
(-
CO)
4
(CO)
2
(PPh
3
)
3
].
MeCN
(dark brown)
(at 173 K)
m
C2/c
4
29.925(1)
16.034(1)
19.495(1)
125.55(1)
PtC
2
P
(x2)
MC
2
P
AuPM
2
(x2)
OC not given
Ph
3
P 2.259(2)
OC not given
OC 1.82(2)
Ph
3
P 2.282(2)
M 2.692(1,4)
Pt 3.356(1)
Au 2.746(1,1)
M 2.896(1)
Au 2.876(1)
not given
not given
not given
[73]
Continued
5
, Pt
2
Cu
3
Fe, Pt
2
M
2
M
2
, and PtOs
3
M
2
)
a
.
COMPOUND
(colour)
Crys.cl
Sp.Grp
Z
a []
b []
c []
a [
o
]
[
o
]
g [
o
]
Chromo-
phore
M-L
[]
M-M []
M-L-M []
L-M-L
[
o
]
Ref
1118
The structure of the red PtAu
5
cluster [55] can be
described as a fragment of a Pt-centered icosahedron.
The central Pt atom is bonded to fve peripheral
AuPPh
3
units. The Pt-Au bonds range from 2.590(3) to
2.676(3) and Au-Au from 2.811(3) to 3.176(3) .
There are nine red PtRu
5
clusters [56-60] of the
general formula (L)PtRu
5
(
6
-C)(-CO)
n
(CO)
m
, in
which six metal atoms are arranged in the form of an
octahedron with the
6
-carbide ligand located in the
center. The Pt-
6
C and Ru-
6
C bond distances are
~2.04 . The PtL (L = CO [56], PBu
t
3
[57], cod [58],
PPh
3
[58], PMe
2
Ph [59], dppe [60] fragment spans
four ruthenium atoms in an unsymmetrical fashion.
The Pt-Ru distances, as well as the Ru-Ru core, are
almost in the same range with values of 2.77 to 3.15
and 2.79 to 3.15 (Table 3A), respectively. Three of
the clusters [56,58,59] contain two crystallographically
independent molecules within the same crystal, differing
mostly by degree of distortion.
In another three red PtRu
5
clusters [57,61,62], fve
ruthenium atoms form a square-pyramidal cluster, the
5
-carbido ligand being located in the center of the
square face with a mean Ru-C-Ru angle of 90.0 ( 8.6).
In monoclinic (PBu
t
3
)PtRu
5
(
5
-C)(-CO)
2
(CO)
13
[57],
which contains two crystallographically independent
molecules, in each the Pt(PBu
t
)
3
fragments only two
Ru atoms are bonded in the base. In addition, each of
Ru-Pt edges is bridged by a CO group. The mean Pt-Ru
bond distances are 2.795 (in molecule 1) and 2.825
(in molecule 2). The mean Ru-Ru bond distances are
2.860 in both molecules. In another monoclinic (CO)
PtRu
5
(
5
-C)(
3
-PhCCPh)(-PhCCPh) cluster [61],
which also contains two crystallographically independent
molecules within the same crystal, the Pt(CO) fragment
caps one Ru
3
triangle. There is a triple bridging PhCCPh
ligand on one of the PtRu
2
triangular groupings and an
edge bringing the PhCCPh ligand across the bond
between the Pt atoms at the apex of the square pyramid.
[Pt
3
(Pt
0.21
Ni
0.79
)
(AuPPh
3
)
2
(-
CO)
4
(CO)
2
(PPh
3
)
2
].
(dark brown)
(at 173 K)
tr
P
2
12.876(1)
13.432(1)
27.051(1)
87.86(1)
88.81(1)
74.20(1)
PtC
2
P
(x3)
MC
3
Au
AuPM
2
(x2)
OC not given
Ph
3
P
OC not given
OC 1.69(2)
Ph
3
P 2.294(2,3)
M 2.670(2,38)
Pt 3.256(1)
Au 2.712(3,18)
Pt 2.917(4)
Au 3.075(1)
not given
not given
not given
[73]
[Pt
3
(Pt
1.36
Ni
0.64
)
(AuPPh
3
)
2
(-
CO)
4
(CO)
2
(PPh
3
)
3
].
MeCN
(dark brown)
(at 173 K)
m
C2/c
4
29.925(1)
16.034(1)
19.495(1)
125.55(1)
PtC
2
P
(x2)
MC
2
P
AuPM
2
(x2)
OC not given
Ph
3
P 2.259(2)
OC not given
OC 1.82(2)
Ph
3
P 2.282(2)
M 2.692(1,4)
Pt 3.356(1)
Au 2.746(1,1)
M 2.896(1)
Au 2.876(1)
not given
not given
not given
[73]
[Pt
3
(Pt
1.58
Ni
0.42
)
(AuPPh
3
)
2
(-
CO)
4
(CO)
2
(PPh
3
)
3
].
MeCN
(dark brown)
(at 173 K)
m
C2/c
4
29.939(1)
16.001(1)
19.502(1)
125.48(1)
PtC
2
P
(x2)
MC
2
P (x2)
AuPM
2
(x2)
OC not given
Ph
3
P 2.258(2)
OC not given
OC 1.82(3)
Ph
3
P 2.285(2)
M 2.679(1,5)
Pt 3.351(1)
Au 2.736(1,7)
M 2.903(1)
Au 2.878(1)
not given
not given
not given
[73]
[Pt
3
(Pt
0.12
Ni
1.88
)
(AuPPh
3
)
2
(-
CO)
4
(CO)
2
(PPh
3
)
3
].
(thf)
(dark brown)
(at 173 K)
m
P2
1
/n
4
12.976(1)
39.978(1)
15.599(1)
97.051(1)
PtC
2
P
(x2)
MC
2
P (x2)
AuPM
2
(x2)
OC not given
Ph
3
P 2.269(3,2)
OC not given
OC 1.71(2,3)
Ph
3
P 2.281(3,2)
M 2.558(1,8)
Pt 3.495(1)
Au 2.650(2,7)
M 2.876(1)
Au 2.876(1)
not given
not given
not given
[73]
[Pt
3
(Pt
0.1
Ni
1.90
)
(AuPPh
3
)
2
(-CO)
4
(CO)
2
(PPh
3
)
3
].
CH
2
Cl
2
(dark brown)
(at 173 K)
m
C2/c
8
47.947(3)
15.763(1)
20.032(1)
96.59(1)
PtC
2
P
(x2)
MC
2
P (x2)
AuPM
2
(x2)
OC not given
Ph
3
P 2.303(3,3)
OC not given
OC 1.76(2,0)
Ph
3
P 2.301(3,1)
M 2.679(1,5)
Pt 3.351(1)
Au 2.736(1,7)
M 2.903(1)
Au 2.878(1)
not given
not given
not given
[73]
c. The average M-M distance.
d. There are two crystallographically independent molecules.
e. There are three crystalografcally independent molecules.
Continued
5
, Pt
2
Cu
3
Fe, Pt
2
M
2
M
2
, and PtOs
3
M
2
)
a
.
COMPOUND
(colour)
Crys.cl
Sp.Grp
Z
a []
b []
c []
a [
o
]
[
o
]
g [
o
]
Chromo-
phore
M-L
[]
M-M []
M-L-M []
L-M-L
[
o
]
Ref
1119
The mean Pt-Ru and Ru-Ru bond distances (molecule
1 vs. molecule 2) are 2.847 and 2.857 vs. 2.854 and
2.911 . The structure of orthorhombic (CO)PtRu
5
(
5
-C)
(
3
-EtCCEt)(-EtCCEt)(CI)
12
[62] is similar to its
PhCCPh analogue [61]. The mean Pt-Ru and Ru-Ru
distances are 2.865 and 2.918 .
In the [PtRh
5
(
3
-CO)
4
(CO)
12
]
2-
anion [63], the metal
atoms form an octahedron with the mean of four
Pt-Rh bonds at 2.790 , which are about 0.030 longer
than those of the eight Rh-Rh bonds (ave 2.760 ).
The Pt-
3
CO bond distance of 2.13(2) is shorter than
the Rh-
3
CO bond with a value of 2.22(2) (ave.).
There are fve PtOs
5
clusters [64-67] (Table 3A).
The structure of monoclinic (PPh
3
)PtOs
5
(
4
-S)(-CO)
(CO)
14
[64] consists of a square pyramidal arrangement
of fve osmium atoms with the sulfde atom located in
the center of the square face. The square pyramid is
capped on one triangular face by a Pt atom. Seven
of the eight Os-Os bond distances lie in the range
2.804(1)-2.919(1) . The bonding of the Pt atom to the
Os atom is very unsymmetric, with a Pt-Os(3) distance
of 2.646(1) and a Pt-Os(2) distance of 2.986(1) .
The structure of triclinic [(PPh
3
)PtOs
5
(
4
-S)
(CO)
15
(PPh
3
)]0.25CH
2
Cl
2
[64,65] consists of a square-
pyramidal arrangement of one platinum and four osmium
atoms with the sulfde atom located in the center of the
square face. The ffth osmium atom bridges the pair
of osmium atoms in the basal plane. The mean Pt-Os
and Os-Os bond distances are 2.870 and 2.848 .
The remaining three PtOs
5
clusters, monoclinic (CO)
PtOs
5
(-H)
4
(CO)
17
[66], triclinic PtOs
5
(
3
-S)(-H)
6
(CO)
15

[66] and monoclinic PtOs
5
(-H)
6
(CO)
15
[67], contain
a PtOs
3
tetrahedron fused to a PtOs
2
triangle by the
vertex-sharing platinum atom. The structure of PtOs
5
(-
H)
6
(CO)
15
is shown in Fig. 8, where it can be seen that
there are six hydride atoms bridging the respective metal
atoms. Triclinic red PtOs
5
(
3
S)(-H)(CO)
15
[66] contains
two crystallographically independent molecules. The
mean Pt-Os and Os-Os bond distances are 2.870
and 2.887 in the monoclinic cluster [66], 2.766 and
2.921 (in triclinic, molecule 1), 2.770 and 2.766
(in triclinic, molecule 2) [66], and 2.739 and 2.887 [67].
The green Pt
2
Cu
3
Fe cluster [68] is the only
example of such a combination of metals in the series
of heterohexanuclear platinum clusters. The six metal
atoms are arranged in a slightly irregular octahedron,
with two platinum atoms mutually trans while three
copper atoms and one iron atom are in the equatorial
plane. Three phenylethynyl ligands are bonded
to each platinum atom and form -linkages to each
of the copper atoms. The average of the Pt-Cu bond
distances is 2.910 . The two coordination planes of
platinum are almost parallel, the dihedral angle being
4.5. The ferrocenediyl moieties have an eclipsed
conformation with a dihedral angle of 7.4 between
them (Table 3A).
Figure 8. Structure of [PtOs
5
(-H)
6
(CO)
16
] [67].

1120
There are two Pt
2
M
2
M
2
clusters, red Pt
2
Co
2
Na
2
[69]
and black Pt
2
W
2
Ru
2
[70] (Table 3C). In the former [69],
a pair of Pt(mec)
4
Co units weakly bind two Na(I) atoms
through their sets of four O(2) donors. Each Na(I) atom
completes its distorted octahedral coordination sphere
by an oxygen from a nitrate anion and an O(2) atom
of the other symmetry-related PtCo unit. Cobalt(III) is
bonded to the four N4 sites of the methylcytosinate
ligands, to platinum and a water molecule. The
platinum(II) atom is surrounded by the four N3 donor
sites. The methylcytosinato ligands around the metals
are distorted in a twisted propeller fashion. All three
metals are in an almost collinear arrangement (Na...
Pt-Co of 175.33(8)) with a Pt-Co bond of 2.402(2) and
a Pt...Na distance of 3.369(5) . In black Pt
2
Ru
2
W
2
(
3
-
tlm)
2
(-CO)
2
(CO)
9
(cp)
2
[70], two
5
-tolylmethylidine
groups span the metal triangles, one W2Ru1Pt1 and the
other W2Ru1Pt2. The mean metal-metal bond distances
elongate in the order: 2.712 (Pt-Ru) < 2.723
(Pt-W) < 2.800 (Ru-W).
There are two PtOs
3
M
2
clusters, orange (M = Sn
[71]) and brown (M = Fe [72]) (Table 3D). The metal
framework in the former may be described as an
edge-bridged tetrahedron, and is shown in Fig. 9. The
tetrahedron comprises a platinum atom plus Sn(1)
and two osmium atoms, Os(2) and Os(3). The
Os(2)-Sn(1) edge is bridged by a third osmium atom
Os(1). The Pt-Sn(1) distance is 2.975(5) which is
longer than the mean Pt-Os(2)/Os(1) bond distance of
2.823 . The Os(1)...Os(3) and Os(1)...Pt separations of
4.500(3) and 4.602(3) rule out the possibility of bonding.
The structure of [(cod)PtOs
3
(CO)
9
(
4
-cpbcp)
Fe
2
(cp)
2
] [72] is shown in Fig. 10, and consists of
a butterfy cluster of metal atoms consisting of one Pt
and three Os atoms. The platinum atom occupies one of
the wingtip positions. The cluster is coordinated to one
of the C-C triple bonds of the FeC
4
Fe ligand in the well-
established
4
-bonding mode. The mean Pt-Os bond
distance of 2.739 is somewhat shorter than the mean
Os-Os distance of 2.780 .
In dark brown, Pt
3
(Pt
1-x
Ni
x
)(AuPPh
3
)
2
(CO)
4
(CO)
(PPh
3
)
3
(1) [73] and Pt
2
(Pt
2-y
Ni
y
)(AuPPh
3
)
2
(-
CO)
4
(CO)
2
(PPh
3
)
2
(2) [73], the six metal atom M
4
Au
2

cores constitute butterfy based geometries, in which
each of the two basal M
B
atoms is coordinated to both
Au atoms of the bidentate {Ph
3
PAu-AuPPh
3
} unit. Both
of these clusters show ligation-induced site-specifc
Pt/Ni substitution disorder at one or both of their basal
M
B
atomic sites. Both clusters exist in four solvated
crystals (Table 3). Formal Ni substitution for Pt is at
only the basal NB site(s) in the crystal composition of
cluster (1) and (2) was found to vary widely from 0.17 to
0.79 Ni in (1) and from 0.42 to 1.90 In in (2). The mean
M-M bond distance (1 vs. 2) elongated in the order:
2.679 vs. 2.633 (Pt-PtB) < 2.724 vs. 2.678 (Au-
MB) < 2.927 vs. 2.855 (PtB-NiB) < 3.032 vs. 2.886
(Au-Au) < 3.274 vs. 3.364 (Pt-Pt).
Examination of the data in Tables 1-3 reveals that
there are seventy-three heterohexanuclear platinum
clusters, with seven different types of composition: Pt
5
M,
Pt
4
M
2
, Pt
3
M
3
, Pt
2
M
4
, PtM
5
, Pt
2
M
3
M and Pt
2
M
2
M
2
, of which
Pt
2
M
4
(24 examples) and PtM
5
(22 examples) are by far
Figure 9. Structure of [(Pcy
3
)PtOs
3
Sn(-H)
2
(Cl)(OEt
2
)(CO)
10
SnCl
3
] [71].

1121
Figure 10. Structure of [(cod)PtOs
3
(CO)
9
(-cpbcp)Fe
2
(cp)
2
] [72].
Table 4. Summary of the mean Pt-M distances in heterohexanuclear platinum clusters.
Pt-M [] bonds
a
Pt-M []
b
Pt-M
Mean Shortest [ref] Longest [ref] Mean Shortest [ref] Longest [ref]
-Ge 2.420 2.395(4)[52] 2.480(3)[52]
-Fe 2.617 2.570(4)[6] 2.910(1)[54] 3.61 3.49(3)[22] 3.69(3)[22]
-Sn 2.626 2.550(1)[53] 2.975(5)[71]
-Li 2.640 2.621(11)[28] 2.658(11)[28]
-Au 2.645 2.590(3)[55] 2.676(3)[55]
-Co 2.677 2.402(2)[69] 2.937(2)[23] 3.060(2)[23]
-Ir 2.680 2.625(3)[24] 2.708(3)[24]
-W 2.727 2.663(3)[70] 2.747(3)[19]
-Hg 2.730 2.648(4)[8] 2.813(3)[11] 3.09 3.015(1)[9] 3.163(3)[11]
-Re 2.750 2.548(2)[7] 2.792(2)[7] 3.275(2)[7]
-Os 2.768 2.605(1)[48] 2.986(1)[64] 3.053
c
3.015(1)[48] 3.092(3)[48]
-Rh 2.790 2.776(2)[63] 2.811(2)[61]
-Ag 2.792 2.746(4)[13] 2.950(1)[36] 3.254 3.034(2)[33] 3.905(3)[14]
-Ru 2.839 2.6456(8)[41] 2.997(2)[62] 3.115 3.045(2)[56] 3.3076(5)[60]
-Cu 2.910 2.845(5)[68] 2.975(5)[68]
-Na 3.369(5)[69]
-Tl 3.498 3.482(1)[31] 3.514[31]
-Pd 6.81(1)[25]
a
Pt-M less 3.0
b
Pt-M over 3.0
c
Pt-Os, 4.602(3) [71] was not included to the mean value

1122
most common. The clusters crystallize in the six crystal
classes: monoclinic (41) > triclinic (22) > orthorhombic
(7) > tetragonal, trigonal and cubic (one each).
Six metal atoms form a wide variety of
stereochemistries, of which octahedral, with different
degrees of distortion, and a square-pyramidal with
capping by the sixth metal are most common. The
(CO)
2
Pt
2
Ru
4
(CO)
16
molecule exists in two isomeric
forms, monoclinic [41] and orthorhombic [42].
Another case, PtOs
5
(
3
-S)(-H)
6
(CO)
15
[66] contains
three crystallographically independent molecules
within the same crystal, and seven other clusters
[24,33,51,56,58,59,61] contain two such molecules.
The isomers and the crystallographically independent
molecules differ mostly by degree of distortion, and all
are examples of distortion isomerism [74].
A summary of the Pt-M bond distances (below
3.0 ) and the Pt-M separations (over 3.0 ) are
gathered in Table 4. Although platinum is classifed as
a soft metal atom, it can be seen that it is found bonded
to a variety of other metal atoms of the soft, borderline
and hard variety. There are nineteen different metal
atoms which are involved in the hexohexanuclear
platinum clusters. These metal atoms are: Ru
(18 examples) < Os(12 examples) < Fe (11 examples) <
Ag (7 examples) < Hg (5 examples) < Pd (4 examples)
< Li, Sn, Re (3 examples each) < Co, W (2 examples
each) < Na, In, Tl, Ge, Cu, Au, Rh, Ir (1 example each).
The shortest Pt-M bond for a non-transition metal is
Pt-Ge with a distance of 2.395(4) [52] and for Pt-M
(transition) it is Pt-Co with a distance of 2.402(2) [69].
A summary of M-M and M-Mdistances for
heterohexanuclear platinum clusters is shown in
Table 5. As can be seen, the shortest M-M bond distance
is an Re-Re triple bond with a distance of 2.2839(5)
[38]. The shortest Pt-Pt bond is 2.5325(6) [44] and the
shortest M-M bond is that of Os-Sn, with a distance of
2.608(5) [71].
3. Conclusions
This review classifed and analyzed over seventy
heterohexanuclear platinum clusters. This review with
its precursors [1-5] shows platinum present with other
metal atoms as partners in molecules from two to six
metal atoms per unit. There are over one thousand and
three hundred such examples, which clearly document
an enormous interest in platinum chemistry. The metal
atoms cover nineteen transition metals, ffteen non-
transition metals, lanthanides (Yb and U), and even an
actinide (Th). These clusters crystallize mostly in three
crystal classes: monoclinic (51,8%) > triclinic (32.5%) >
orthorhombic (13.7%).
Interestingly, the shortest Pt-Pt bond of 2.58 is
present in hetero-trimers, -tetramers, -and pentamers.
This bond in heterohexamers is somewhat stronger
with a distance of 2.532 . The shortest Pt-M (non-
transition) bond distance elongates in the order:
2.315 (M = Ga, trimers) < 2.354 (Ge, dimers) <
2.395 (Ge, hexamers) < 2.406 (Ge, pentamers) <
2.430 (Ge, tetramers). The shortest Pt-M (transition)
bond distance elongates in the order: 2.402 (M =
Co, hexamers) < 2.483 (Pd, tetramers) < 2.489
(Co, trimers) < 2.495 (Cr, dimers) < 2.500 (Co,
pentamers).
It is hoped that this review will serve to organize the
majority of relevant structural information on platinum
in a systematically useful manner and illustrate the
similarities and differences which may be important,
serving to stimulate further studies in this rich area
of chemistry. A similar review of heteroheptanuclear
platinum clusters is in progress.
Table 5. Summary of the mean M-M and M-M distances in
heterohexanuclear platinum clusters.
M-M []
M - M
Mean Shortest [ref] Longest [ref]
Re Re 2.2839(5)[38] 13.26(2)[28]
Co Co 2.692 2.691(3)[23] 2.693(1)[23]
Fe Fe 2.693 2.622(2)[54] 2.786(1)[54]
Pt Pt 2.727 2.5325(6)[44] 2.9489(9)[9]
3.372 3.008(1)[10] 3.714(2)[10]
7.273 6.949(1)[55] 7.88(1)[25]
Li Li 2.746 2.57(4)[29] 2.91(2)[28]
Rh Rh 2.760 2.698(2)[63] 2.827(1)[63]
Os Os 2.846 2.530(1)[50] 2.989(1)[65]
3.062 3.002(3)[71] 3.092(1)[48]
4.500(3)[71]
Au Au 2.858 2.811(5)[55] 2.935(3)[55]
3.070 3.005(4)[55] 3.176(3)[55]
Pd Pd 2.865 2.853(2)[51] 2.877(2)[51]
3.45 3.39(1)[25] 3.51(1)[25]
Ru Ru 2.875 2.664(2)[62] 2.965(2)[56]
3.054 3.000(1)[45] 3.129(2)[62]
Ag Ag 2.887 2.815(4)[14] 2.959(2)[34]
6.898(1)[37]
Hg Hg 3.506 3.395(4)[11] 3.617(1)[10]
Tl Tl 4.254 4.238[31] 4.270[31]
Sn Os 2.622 2.608(5)[71] 2.645(5)[71]
3.058(3)[71]
W Ru 2.800 2.757(5)[70] 2.843(5)[70]
1123
C.E. Holloway, M. Melnk, Centr. Eur. J. Chem. 9,
501 (2011)
M. Melnk, O. Spruansk, C.E. Holloway, Centr.
Eur. J. Chem. 10, 1709 (2012)
M. Melnk, P. Miku, C.E. Holloway, Centr. Eur.
J. Chem. 11, 827 (2013)
M. Melnik, P. Miku, C.E. Holloway, Centr. Eur.
J. Chem. 11, 1902 (2013)
M. Melnk, P. Miku, C.E. Holloway, Centr. Eur.
J. Chem. 12, 283 (2014)
Abbreviations
abz 2-SC
6
H
4
N = C(H)C
5
H
4
;
ac acetate;
acac acetylacetonate;
ampy 2-aminopyridinate;
betmp bis(ethylthio)methylenepropanedioate;
bpeb o-bis(phenylethynyl)benzene;
bpy 2,2-bipyridine;
bpyv 4,4di(cyclopentadienyl)vinyl-2,2-bipyridine;
bpz 2,2-bipyrazine;
C
6
Cl
5
pentachlorophenyl;
C
6
F
5
pentafuorophenyl;
cod cycloocta-1,5-diene;
cp cyclopentadienyl;
cp* pentamethylcyclopentadienyl;
C^P -CH
2
C
6
H
4
P(o-tolyl)
2
;
C
5
H
10
pentane;
C
5
H
4
PPh
2
diphenylcyclopentadienylphosphine;
cpbcp bis(cyclopentadienyl)butadiyne;
EtCCEt 1,2-diethyletin;
PhCCPh 1,2-diphenyletin;
dach diaminocyclohexane;
dbbpy 4,4-di-tert-butyl-2,2-bipyridine;
dppe 1,2-bis(diphenylphosphine)ethane;
dppm bis(diphenylphosphino)methane;
en ethylenediamine;
Et ethyl;
m monoclinic;
Me methyl;
mec 1-methylcytosinate;
meu methyluracilate;
NMe
4
tetramethylammonium;
or orthorhombic;
PPh
3
triphenylphosphine;
PMe
3
trimethylphosphine;
Pcy
3
tricyclohexylphosphine;
PEt
3
triethylphosphine;
Ph phenyl;
P(mop)
3
tri(p-methoxyphenyl)phosphine;
PBu
t
3
tri-tert-butylphosphine;
PPr
i
3
tri-iso-propylphosphine;
tlm 4-tolylmethylidyne;
thf tetrahydrofuran.
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1.

anion {Pt-O-Re, 163.8(7)}.

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