The carbodiphosphorane-CS2 adduct as a complex ligand: Crystallographic characterization of [I2Pt{S2CC(PPh3)2}] · CH2Cl2, [Pt{S2CC(PPh3)2}2][SiF5 ]2

Article abstract of DOI:10.1016/j.poly.2008.05.003

The betain-like compound S₂CC(PPh₃)₂ (1), which is obtained from CS₂ and the double ylide C(PPh₃)₂, reacts with [X₂Pt(COD)] (X = Cl, I) in THF to afford the complexes [X₂Pt{S₂CC(PPh₃)₂}] (2, X = Cl; 3, X = I) in quantitative yields. Both compounds are insoluble in all usual solvents, and 3 could be characterized by an X-ray analysis. For comparison, the structures of [Pt(Me)₂FI{S₂CC(PPh₃)₂}] · 2CH₂Cl₂ (4 · 2CH₂Cl₂) with Pt^IV and [Pt{S₂CC(PPh₃)₂}₂][SiF₅ ]₂ · 2CH₂Cl₂ (5 · 2CH₂Cl₂) with Pt^II are also presented. The compounds are further characterized by ³¹P NMR and IR spectroscopy.

Full text of DOI:10.1016/j.poly.2008.05.003

Polyhedron 27 (2008) 2539–2544
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Polyhedron
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The carbodiphosphorane–CS2 adduct as a complex ligand: Crystallographic
characterization of [I2Pt{S2CC(PPh3)2}] ꢀ CH2Cl2, [Pt{S2CC(PPh3)2}2][SiF5]2 ꢀ 2CH2Cl2
and [(Me)2PtFI{S2CC(PPh3)2}] ꢀ 2CH2Cl2
*
*
Wolfgang Petz , Bernhard Neumüller
Fachbereich Chemie der Philipps-Universität, 35032 Marburg, Germany
a r t i c l e i n f o
a b s t r a c t
Article history:
The betain-like compound S2CC(PPh3)2 (1), which is obtained from CS2 and the double ylide C(PPh3)2,
reacts with [X2Pt(COD)] (X = Cl, I) in THF to afford the complexes [X2Pt{S2CC(PPh3)2}] (2, X = Cl;
3, X = I) in quantitative yields. Both compounds are insoluble in all usual solvents, and 3 could be char-
acterized by an X-ray analysis. For comparison, the structures of [Pt(Me)2FI{S2CC(PPh3)2}] ꢀ 2CH2Cl2
(4 ꢀ 2CH2Cl2) with PtIV and [Pt{S2CC(PPh3)2}2][SiF5]2 ꢀ 2CH2Cl2 (5 ꢀ 2CH2Cl2) with PtII are also presented.
The compounds are further characterized by 31P NMR and IR spectroscopy.
Received 17 March 2008
Accepted 6 May 2008
Available online 16 June 2008
Keywords:
Betain-like compounds
Carbodiphosphorane adducts
Chelating ligand
Ó 2008 Elsevier Ltd. All rights reserved.
Crystal structures
Platinum compounds
6þ
4þ
1. Introduction
Ag6 or Ag4 clusters are held together by six or four molecules
of 1, respectively, and each S atom contacts up to two Ag atoms
[6]. The S2C–CP2 bond length in 1 is shorter than a single bond
and further shortening occurs upon complex formation, indicating
an increase of bond strength. Calculations have shown that in 1
The Lewis acid CS2 and the carbodiphosphorane C(PPh3)2 quan-
titatively form the yellow addition compound S2CC(PPh3)2 (1),
which has been known for many years [1]. In addition to 1, further
adducts with Lewis acids containing main group [2] or transition
metal elements [3] were also described. Recently, we have studied
the crystal structure of 1 and its ability as a possible complex
ligand.
some
p interaction exists between the occupied p orbital of the
P2C sp2 carbon atom and the empty p orbital of the S2C sp2 carbon
atom [4]. In this publication, we present the results of the reaction
of 1 with some platinum complexes.
S
S
PPh3
PPh3
2. Results and discussion
C
C
Reactions of 1 turned out to be highly problematic because 1 is
only slightly soluble in THF and insoluble in the usual non-polar
solvents, and it decomposes at elevated temperatures or upon pro-
longed reaction time to give SPPh3 and the heterocummulene
1
S@C@C@PPh3 [7]. Compound 1 is soluble in CH2Cl2 (
31P NMR in
CH2Cl2: 17.11 ppm), but decomposition proceeds more rapidly in
this solvent. However, in some cases the reaction products are sol-
uble in THF, which allows sufficient characterization [4].
If a suspension of 1 in THF is treated with the platinum com-
plexes [X2Pt(cod)] (X = Cl, I) reaction immediately occurs to pro-
duce red-brown precipitates of 2 and 3, respectively, with release
of COD. Both products are obtained in about quantitative yields
according to the following equation:
Thus, in [M(CO)6] (M = Cr, Mo, W) two carbonyl groups can be
replaced to produce the corresponding [(CO)4M{S2CC(PPh3)2}]
complexes, in which 1 acts as a chelating ligand via the two sulfur
atoms [4]. The same is true for cationic manganese and cobalt com-
plexes [5]. An alternative coordination mode of 1 was found upon
reaction with silver salts containing weakly coordinating anions;
* Corresponding authors. Fax: +49 6421 2825653.
E-mail addresses: petz@staff.uni-marburg.de (W. Petz), neumuell@chemie.uni-
marburg.de (B. Neumüller).
½X2PtðCODÞꢁ þ S2CCðPPh3Þ2 ! ½X2PtfS2CCðPPh3Þ2gꢁ þ COD
ð1Þ
0277-5387/$ - see front matter Ó 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.poly.2008.05.003

2540
W. Petz, B. Neumüller / Polyhedron 27 (2008) 2539–2544
X
X
S
S
PPh3
PPh3
Pt
C
C
2 (X= Cl), 3 (X= I)
The new platinum complexes 2 and 3 are found to be insoluble
in all common solvents including THF and CH2Cl2, but are slightly
soluble in DMSO. If amorphous 3 from THF is kept in contact with
CH2Cl2 a kind of mineralization proceeds and the precipitate takes
up dichloromethane and is converted into small red crystals. How-
ever, the overstanding solution shows no signal in the 31P NMR
spectrum confirming the insolubility in this solvent. Unfortunately,
no crystals of 2 could be obtained via this way. In the 31P NMR
spectra in DMSO singlets at 14.6 ppm (for 2) and 14.0 ppm (for
3) were recorded. The solid state IR spectra of 2 and 3 are very sim-
ilar and contain the same number of bands, which indicate analo-
gous structural properties. Strong absorptions at about 1049 and
1095 cmꢂ1 were recorded, which can be assigned to the mas and
ms CS2 vibrations [8]. The related bands in 1 were found at 1067
and 1099 cmꢂ1. A strong band at 1250 cmꢂ1 in both compounds
can probably be attributed to the vibration of the S2C–CP2 bond
of the ligand. According to the occupied p orbital at the P2C carbon
atom and the vacant p orbital at the S2C carbon atom, additional to
Fig. 1. Molecular structure of 3 ꢀ CH2Cl2 showing the atom numbering scheme. The
ellipsoids are drawn at a 40% probability level; the H atoms at the phenyl rings and
the CH2Cl2 molecule are omitted for clarity.
the
r donor bond a weak and polarized p-interaction is operative
[4]. The related band in 1 is found at 1146 cmꢂ1 and the shift to
higher frequencies upon complex formation can be explained with
an increase of the C–C double bond character, which is also ex-
pressed in a shorter C–C bond length in 3.
Additionally, we present the crystal structures of two further
compounds with the ligand 1 for comparison. Crystals of the com-
plexes [(Me)2PtFI{S2CC(PPh3)2}] ꢀ 2CH2Cl2 (4 ꢀ 2CH2Cl2) and
[Pt{S2CC(PPh3)2}2][SiF5]2 ꢀ 2CH2Cl2 (5 ꢀ 2CH2Cl2) were obtained by
reacting 1 with a sample of an impure platinum compound which
was formed as a result from attempts to fluorinate [Me2Pt(cod)]
(still containing some [Me(I)Pt(cod)]) with XeF2; the complex
[(CF3)2Pt(cod)] was expected [9]. The anion [SiF5]ꢂ may originate
from fluorination of some glass or grease by XeF2.
3. Crystal structures
To get more insight into the nature of the complexes and the
bonding situation an X-ray analysis of 3 was performed. Small dark
red crystals of 3 ꢀ CH2Cl2 suitable for an X-ray analysis formed in a
suspension of the powder in CH2Cl2 at room temperature. To our
knowledge, no other platinum(II) compounds with an I2PtS2
arrangement are known in which the sulfur atoms come from a
CS2 adduct of the type S2CR; only two PtIV complexes with a dithio-
carbaminato ligand have been characterized by X-ray analyses
[10]. PtII compounds with this core are described with thiourea
derivatives [11], with dimethylsulfoxide [12] or with thioethers
[13]. PtII complexes with other zwitterionic compounds are de-
scribed with the ligand S2CPR3 [14]. For comparison we include
the structures of 4 ꢀ 2CH2Cl2 and 5 ꢀ 2CH2Cl2, which we have ob-
tained as described above. The molecular structures of 3 ꢀ CH2Cl2,
4 ꢀ 2CH2Cl2, and of the cation of 5 ꢀ 2CH2Cl2 are depicted in Figs.
1–3. Crystallographic data are listed in Table 1, and distances and
angles are summarized in Tables 2–4.
Fig. 2. Molecular structure of 4 ꢀ 2CH2Cl2 showing the atom numbering scheme.
The ellipsoids are drawn at a 40% probability level; the H atoms at the phenyl rings
and the CH2Cl2 molecules are omitted for clarity.
structure is shown in Fig. 1; the solvent molecule is omitted. On
complex formation the ligand 1 undergoes some remarkable
changes. The S2C–CP2 bond length decreases from 149.4(2) to
141(2) pm indicating an increased double bond character, and to-
gether with the S2C–CP2 bond lengths of 5 it is the shortest one
found in complexes of 1. The P–C distances to the ylidic carbon
atom are slightly longer (mean 178 pm) than those in 1; only the
mean P–CPh distances are the same as in the free ligand. A slight
elongation of the C–S bond length is also observed. These changes
in bond lengths upon complex formation can be interpreted in
terms of a release of
p electron density away from the ylidic carbon
atom; the same trends were found in the (CO)4M adducts [4]. The
S–Pt–S angle amounts to 74° and is larger than the corresponding
S–M–S angle in the group 6 metal carbonyl derivatives, whereas
the S–C–S bite angle is smaller (106°); in going from 1 to 3 a de-
crease of the bite angle of about 18° occurs, indicating the great
3.1. Crystal structure of 3 ꢀ CH2Cl2
The environment of the platinum atom is planar as shown by
the sum of the bond angles at the Pt atom of 360°; the crystal

W. Petz, B. Neumüller / Polyhedron 27 (2008) 2539–2544
2541
Fig. 3. Molecular structure of the cation of 5 ꢀ 2CH2Cl2 omitting the solvent molecules and showing the atom numbering scheme. The ellipsoids are drawn at a 50% probability
level; the phenyl groups are represented as thin lines omitting the H atoms for clarity.
Table 1
Crystal data and structure refinement details for the compounds 3 ꢀ CH2Cl2, 4 ꢀ 2CH2Cl2 and 5 ꢀ 2CH2Cl2
3 ꢀ CH2Cl2
4 ꢀ 2CH2Cl2
5 ꢀ 2CH2Cl2
Formula
mw (g/mol)
a (pm)
b (pm)
c (pm)
C39H32Cl2I2P2PtS2
1146.56
1104.6(1)
1832.1(2)
1965.9(3)
90
C42H40Cl4FIP2PtS2
1153.66
1105.0(1)
1252.0(2)
1766.4(2)
71.30(1)
C78H64Cl4F10P4PtS4Si2
1836.57
1442.1(2)
1567.7(2)
1829.8(2)
71.10(2)
a
(°)
b (°)
(°)
101.88(1)
90
76.38(1)
74.84(1)
82.34(2)
80.40(2)
c
Crystal size (mm)
Volume (pm3 ꢃ 106)
Z
0.08 ꢃ 0.04 ꢃ 0.02
3893.2(8)
4
0.29 ꢃ 0.2 ꢃ 0.05
2203.2(5)
2
0.18 ꢃ 0.13 ꢃ 0.04
3845.0(8)
2
dcalc (g/cm3)
Crystal system
Space group
Diffractometer
Radiation
1.956
1.739
1.586
monoclinic
P21/c (nr. 14)
IPDS II (Stoe)
triclinic
triclinic
ꢀ
ꢀ
P1 (nr. 2)
P1 (nr. 2)
IPDS I (Stoe)
IPDS I (Stoe)
Mo Ka
Mo K
193
a
Mo K
193
a
Temperature (K)
193
55.4
l
(cmꢂ1
)
43.3
22.5
2hmax (°)
52.50
52.24
52.25
Index range
ꢂ13 6 h 6 13, ꢂ22 6 k 6 22,
ꢂ24 6 l 6 24
26549
ꢂ12 6 h 6 12, ꢂ15 6 k 6 15,
ꢂ21 6 l 6 21
21835
ꢂ17 6 h 6 17, ꢂ19 6 k 6 19,
ꢂ21 6 l 6 21
38256
Number of reflections collected
Number of independent reflections (Rint
Number of observed reflections with
)
7699 (0.2251)
3548
8068 (0.0674)
5542
14085 (0.235)
4186
F0 > 4r(F0)
Parameters
434
490
706
Absorption correction
Structure solution
Refinement against F2
H atoms
numerical
direct methods SIR-92 [19]
numerical
direct methods SIR-92 [19]
numerical
Patterson method SHELXTL-Plus [20]
SHELXL-97 [21]
SHELXL-97 [21]
SHELXL-97 [21]
a
a
a
R1
0.0762
0.1625
1.18
0.059
0.1589
5.28
0.066
0.1441
1.18
wR2 (all data)
Maximum electron density left (e/
pm3 ꢃ 10ꢂ6
)
a
Calculated positions with common displacement parameter.
flexibility of this angle according to the nature of the central metal
atom. The dihedral angle between the S2C and the P2C planes
amounts to 26° and is larger than that in the free ligand 1 (20°).
The increased deviation from planarity may be due to interactions
of the sulfur atoms with phenyl rings in such that one ring at P(1) is
pushing up the sulfur atom S(1) and another one at P(2) is pushing
down the S(2) atom, and the shorter S2C–CP2 bond in 3 relative to
the free ligand brings the phenyl groups closer to the sulfur atoms
which causes a further increase of the repulsion. The Pt–I distances
(mean 262.5(1) pm) and the Pt–S distances (mean 229.2(4) pm)
are typical for compounds of PtII with a PtS2I2 core and a cis
arrangement of the I atoms; the same is true for the I–Pt–I angle
[13a,13b,13c,13d,13e,13f,13g].
3.2. Crystal structure of 4 ꢀ 2CH2Cl2
The neutral complex 4 contains PtIV in a distorted octahedral
environment; the crystal structure is depicted in Fig. 2. Other PtIV
compounds with the PtS2 core are equipped either with dithiocar-
baminato ligands [10] or pincer ligands with S donor atoms [15]. In
4 the dihedral angle between the S2C and the P2C planes amounts
to 35° and is larger than that in 3. The S2C–CP2 bond length is in

2542
W. Petz, B. Neumüller / Polyhedron 27 (2008) 2539–2544
Table 2
Table 4
Selected bond lengths (pm) and angles (°) in 3 ꢀ CH2Cl2
Selected bond lengths (pm) and angles (°) in the cation of 5 ꢀ 2CH2Cl2
Bond lengths
Bond lengths
Pt(1)–S(1)
Pt(1)–S(3)
S(1)–C(2)
S(3)–C(40)
P(1)–C(1)
P(1)–C(9)
P(2)–C(1)
P(2)–C(27)
P(3)–C(39)
P(3)–C(47)
P(4)–C(65)
C(1)–C(2)
Pt(1)–I(1)
Pt(1)–S(1)
S(1)–C(2)
P(1)–C(1)
P(1)–C(9)
P(2)–C(1)
P(2)–C(27)
C(1)–C(2)
262.2(2)
228.9(4)
176(2)
180(2)
181(2)
175(2)
182(2)
141(2)
Pt(1)–I(2)
Pt(1)–S(2)
S(2)–C(2)
P(1)–C(3)
P(1)–C(15)
P(2)–C(21)
P(2)–C(33)
262.8(1)
229.5(5)
170(2)
186(2)
181(2)
180(2)
183(2)
231.9(4)
230.8(4)
173(2)
174(2)
174(2)
180(2)
179(2)
181(2)
179(2)
180(2)
181(2)
141(2)
Pt(1)–S(2)
Pt(1)–S(4)
S(2)–C(2)
S(4)–C(40)
P(1)–C(3)
P(1)–C(15)
P(2)–C(21)
P(2)–C(34)
P(3)–C(41)
P(3)–C(53)
P(4)–C(71)
C(3)–C(4)
228.9(4)
229.8(5)
175(2)
174(2)
181(2)
181(2)
180(2)
182(2)
182(2)
180(2)
180(2)
139(2)
Bond angles
I(1)–Pt(1)–I(2)
I(1)–Pt(1)–S(2)
I(2)–Pt(1)–S(2)
Pt(1)–S(1)–C(2)
C(1)–P(1)–C(3)
C(1)–P(1)–C(15)
C(3)–P(1)–C(15)
C(1)–P(2)–C(21)
C(1)–P(2)–C(33)
C(21)–P(2)–C(33)
P(1)–C(1)–P(2)
P(2)–C(1)–C(2)
S(1)–C(2)–C(1)
92.93(5)
169.7(1)
97.2(1)
I(1)–Pt(1)–S(1)
I(2)–Pt(1)–S(1)
S(1)–Pt(1)–S(2)
Pt(1)–S(2)–C(2)
C(1)–P(1)–C(9)
C(3)–P(1)–C(9)
C(9)–P(1)–C(15)
C(1)–P(2)–C(27)
C(21)–P(2)–C(27)
C(27)–P(2)–C(33)
P(1)–C(1)–C(2)
S(1)–C(2)–S(2)
S(2)–C(2)–C(1)
95.8(2)
171.3(2)
74.1(2)
89.3(6)
90.4(6)
Bond angles
107.6(8)
113.1(9)
105.4(8)
113.3(8)
115.3(8)
105.7(8)
125.1(1)
118.(1)
113.6(9)
110.9(9)
105.9(8)
108.5(9)
106.8(7)
106.8(8)
117.(1)
S(1)–Pt(1)–S(2)
S(1)–Pt(1)–S(4)
S(2)–Pt(1)–S(4)
Pt(1)–S(1)–C(2)
Pt(1)–S(3)–C(40)
C(1)–P(1)–C(3)
C(1)–P(1)–C(15)
C(3)–P(1)–C(15)
C(1)–P(2)–C(21)
C(1)–P(2)–C(34)
C(21)–P(2)–C(34)
C(39)–P(3)–C(41)
C(39)–P(3)–C(53)
C(41)–P(3)–C(53)
C(39)–P(4)–C(59)
C(39)–P(4)–C(71)
C(59)–P(4)–C(71)
P(1)–C(1)–P(2)
P(2)–C(1)–C(2)
S(1)–C(2)–C(1)
P(3)–C(39)–P(4)
P(4)–C(39)–C(40)
S(3)–C(40)–C(39)
74.2(2)
S(1)–Pt(1)–S(3)
S(2)–Pt(1)–S(3)
S(3)–Pt(1)–S(4)
Pt(1)–S(2)–C(2)
Pt(1)–S(4)–C(40)
C(1)–P(1)–C(9)
C(3)–P(1)–C(9)
C(9)–P(1)–C(15)
C(1)–P(2)–C(27)
C(21)–P(2)–C(27)
C(27)–P(2)–C(34)
C(39)–P(3)–C(47)
C(41)–P(3)–C(47)
C(47)–P(3)–C(53)
C(39)–P(4)–C(65)
C(59)–P(4)–C(65)
C(65)–P(4)–C(71)
P(1)–C(1)–C(2)
S(1)–C(2)–S(2)
107.6(2)
178.1(2)
74.1(2)
89.9(5)
90.1(6)
178.3(2)
104.2(2)
89.6(6)
89.8(5)
111.4(5)
110.3(4)
103.7(2)
110.0(5)
106.2(5)
112.4(2)
108.1(5)
110.1(6)
112.7(2)
112.8(5)
118.8(5)
108.5(2)
128.2(7)
115(1)
110.8(5)
109.0(2)
111.4(2)
116.5(5)
105.9(2)
105.8(2)
117.6(5)
105.5(2)
102.9(2)
112.4(6)
105.4(2)
108.7(2)
117.1(1)
106.2(8)
127(1)
106.1(9)
129.(1)
125.(1)
Table 3
Selected bond lengths (pm) and angles (°) in 4 ꢀ 2CH2Cl2
Bond lengths
Pt(1)–I(1)
Pt(1)–S(2)
Pt(1)–F(12)
Pt(1)–C(40)
S(2)–C(2)
P(1)–C(3)
P(1)–C(15)
P(2)–C(21)
P(2)–C(33)
278.2(1)
243.7(2)
210(1)
Pt(1)–S(1)
Pt(1)–F(11)
Pt(1)–C(39)
S(1)–C(2)
P(1)–C(1)
P(1)–C(9)
P(2)–C(1)
P(2)–C(27)
C(1)–C(2)
248.0(2)
198(1)
205(1)
171.4(8)
174.1(8)
180.6(8)
175.8(8)
183.8(8)
145(1)
127(1)
S(2)–C(2)–C(1)
208(1)
129.2(9)
116(1)
127(1)
P(3)–C(39)–C(40)
S(3)–C(40)–S(4)
S(4)–C(40)–C(39)
114(1)
106.0(9)
127(1)
170.7(9)
181.7(8)
181.1(8)
181.1(8)
180.5(8)
Bond angles
I(1)–Pt(1)–S(1)
I(1)–Pt(1)–F(11)
I(1)–Pt(1)–C(39)
S(1)–Pt(1)–S(2)
S(1)–Pt(1)–F(12)
S(1)–Pt(1)–C(40)
S(2)–Pt(1)–F(12)
S(2)–Pt(1)–C(40)
F(11)–Pt(1)–C(39)
F(12)–Pt(1)–C(39)
C(39)–Pt(1)–C(40)
Pt(1)–S(2)–C(2)
C(1)–P(1)–C(9)
C(1)–P(2)–C(27)
P(1)–C(1)–C(2)
S(1)–C(2)–S(2)
S(2)–C(2)–C(1)
93.10(6)
156.4(4)
90.2(4)
70.99(8)
92.2(4)
99.7(4)
89.3(4)
169.8(4)
76.6(6)
85.0(6)
90.2(6)
88.6(3)
115.5(4)
111.9(4)
119.8(6)
113.2(5)
123.5(7)
I(1)–Pt(1)–S(2)
I(1)–Pt(1)–F(12)
I(1)–Pt(1)–C(40)
S(1)–Pt(1)–F(11)
S(1)–Pt(1)–C(39)
S(2)–Pt(1)–F(11)
S(2)–Pt(1)–C(39)
F(11)–Pt(1)–C(40)
F(12)–Pt(1)–C(40)
Pt(1)–S(1)–C(2)
C(1)–P(1)–C(3)
C(1)–P(1)–C(15)
C(1)–P(2)–C(21)
C(1)–P(2)–C(33)
P(1)–C(1)–P(2)
P(2)–C(1)–C(2)
S(1)–C(2)–C(1)
94.33(6)
174.3(4)
90.3(4)
103.5(5)
169.5(4)
106.9(4)
98.9(4)
70.6(6)
86.9(6)
87.0(3)
109.7(4)
110.3(4)
113.2(4)
113.0(4)
125.4(5)
114.8(6)
123.3(7)
Fig. 2. The Pt–I distance amounts to 278.2(1) pm and is longer than
in other PtIV compounds with a related ligand arrangement [15]. It
is about 16 pm longer than that in 3 to PtII but 5 pm shorter than
the related distance in the tetrameric [Me3PtI] with a bridging I
atom [16]. If we compare terminal and bridging F atoms as in 4
and [Me3PtF]4, respectively, the terminal one is about 20 pm short-
er [17]. The methyl groups are in trans position to the sulfur atoms
and the Pt–C distances are in the upper range of those in [Me3PtX]4
complexes [16,17].
3.3. Crystal structure of 5 ꢀ 2CH2Cl2
The crystal structure of the dication 5 is shown in Fig. 3. One of
the solvent molecules is disordered. The complex contains two
molecules of 1 at PtII as chelating ligands. The dihedral angles
between the S2C and the P2C planes amount to 19° and 9°,
respectively; the environment at the central Pt atom is planar as
shown by the sum of the angles of 360.1°, and the deviations
of the five atoms from the best plane are very small (Pt(1),
S(1),S(2),S(3),S(4) = ꢂ1,0,1,0,1 pm). The S2C–CP2 bond lengths
are identical with those of 3; similarly, the S–C–S bite angles and
the S–Pt–S angles correspond to those of 3. The mean Pt–S distance
is only slightly longer than that in 3, but the individual distances
differ by about 3 pm, probably due to packing effects. Although
compounds with a PtS4 core are very common in platinum chem-
istry, cationic compounds with a spiro bicyclic CS2PtS2C arrange-
ment have not yet been described. No nearer contacts exist
between the cation and the anions. The Si–F distances in the [SiF5]ꢂ
anions range between 153(1) and 160(1) pm at Si(1) and 152(1)
and 162(1) pm at Si(2).
between that of 1 and 3 amounting to 145(1) pm. The Pt–S bond
lengths are up to 20 pm longer than in the PtII compounds 3 and
5, while the C–S distances are only slightly shorter and close to that
of the free ligand 1. The higher charge at the central atom causes
the S–C–S bite angle to increase and the S–Pt–S angle to decrease
by about 7° and 3°, respectively, relative to the Pt(II) compounds.
The F atom is disordered with a 0.5–0.5 distribution, and F(12)
occupies more exactly the axial octahedron position while F(11)
is slightly bent away from the S atoms. The distance between
F(11) and F(12) is about 67 pm. According to our X-ray data there
is no possibility to introduce a disorder between the positions of
the methyl groups and the fluorine atoms because of the displace-
ment parameters which fit only to the arrangement shown in

W. Petz, B. Neumüller / Polyhedron 27 (2008) 2539–2544
2543
5.1. Preparation of [Cl2Pt{S2CC(PPh3)2}] (2)
4. Conclusion
To a suspension of 520 mg (0.85 mmol) of S2CC(PPh3)2 (1) in
about 40 ml THF was added 320 mg (0.85 mmol) [Cl2Pt(cod)].
The yellow suspension immediately turned red-brown. The mix-
ture was stirred magnetically for about 1 h. Then the precipitate
was filtered, washed with 1 ml THF and dried in vacuum. Yield
710 mg (95%). 31P NMR (DMSO): 14.56 ppm. IR (Nujol): 1585 vw,
1497 m, 1438 s, 1253 vs, 1197 w, 1163 w, 1098 s, 1069 w, 1043
m, 1027 w, 998 m, 811 m, 749 m, 736 w, 721 m, 714 w, 690 s,
564 w, 556 w, 524 s, 506 s, 492 m (cmꢂ1). Anal. Calc. for
[Cl2Pt{S2CC(PPh3)2}] (2): C, 51.94; H, 3.44. Found: C, 50.38; H
3.65%.
In contrast to the carbodiphosphorane adducts of CO2 and COS,
which adopt
only as a chelating ligand towards transition metals as yet. If 1 is
g g
1 or 2 coordination, the CS2 adduct 1 is found to act
connected to Ag+, aggregates of Ag4 or Ag6 cluster units are
held together by the sulfur atom bonded each to one or two silver
atoms [6]. For comparison, the most relevant bond lengths in the
compounds 1 and 3–5 are summarized in Table 5. Whereas in
the starting adduct 1 the S2C–CP2 distance is already shorter than
a single bond, a further shortening is observed upon complex for-
mation, indicating an increase in double bond character. In the PtII
complexes the related S2C–CP2 distances are the shortest ones
found as yet with 141(2) pm; they are close to those in aromatic
4þ
6þ
ring systems. This electron release diminishes the P–C (p–r
*) inter-
5.2. Preparation of [I2Pt{S2CC(PPh3)2}] (3)
action leading to longer distances. This trend was also observed in
the related carbonyl complexes [(CO)4MS2CC(PPh3)2] where S2C–
CP2 distances of about 145 pm were found [4]; similar values are
also recorded in the silver clusters [6].
In a similar procedure as outlined for the preparation of 2, the
red-brown complex 3 was obtained from 0.66 g (1.08 mmol)
[I2Pt(cod)] and 0.60 g (1.08 mmol) of S2CC(PPh3)2 (1). The dry
red-brown powder was treated with CH2Cl2 which produced small
dark red crystals of 3 ꢀ CH2Cl2 during several hours; yield 1.05 g
(92%). 31P NMR (DMSO): 13.96 ppm. IR (Nujol): 1586 vw, 1481
m, 1439 s, 1246 vs, 1192 w, 1163 w, 1096 s, 1073 w, 1049 s,
1024 w, 997 m, 806 m, 740 m, 723 m, 711 w, 693 s, 685 s, 570
Thus, the occupied p orbital of the sp2 CP2 carbon atom in 1 and
the vacant p orbital at the sp2 CS2 carbon atom form a partial dou-
ble bond which, depending on the nature and charge of the metal,
is increased upon coordination of the sulfur atoms at a metal atom.
For the first time, we can compare compounds in which 1 is
bonded to a metal in different oxidation states. There is a great dif-
ference in the coordination of 1 to a PtII or PtIV atom with a planar
or and octahedral ligand arrangement, respectively. In spite of the
higher charge of the central atom in 4 with PtIV a minor electron
release is found, expressed by a longer S2C–CP2 bond accompanied
by about 16 pm longer (mean) Pt–S distances. The differences in
the bonding parameters indicate a weaker bond of the chelating li-
gand 1 in the complex 4. Thus, the S2C–CP2 double bond character
increases in the series 1 < 4 < 3–5 corresponding to a decrease of
the P–C double bond character in this row. Because 5 is the result
of PtII with weakly coordinating anions, further studies in this field
are in progress. Furthermore, the coordination of 1 at PtIV com-
pounds will also be of interest and the formation of cations with
more than one neutral ligand 1, such as compounds with [PtS4X2]2+
or [PtS6]4+ cores, will be a challenge for the future.
w, 553 w, 522 s, 509 s, 494
[I2Pt{S2CC(PPh3)2}] (3): C, 42.99; H, 2.85. Found: C, 41.64; H, 2.91%.
m
(cmꢂ1). Anal. Calc. for
5.3. Formation of [Me2FIPt(S2CC(PPh3)2)] (4) and
[Pt(S2CC(PPh3)2)2][SiF5]2 (5)
An impure sample obtained from fluorination of [Me2Pt(cod)/
I2Pt(cod)] with XeF2 was used [9] for the reaction with 1 in CH2Cl2;
the anion [SiF5]ꢂ may originate from fluorination of glass or grease.
Few crystals of 4 (small red blocks) and 5 (orange plates) were ob-
tained from CH2Cl2 solutions upon layering with n-pentane; no
further crystalline product was formed. Compound 4, 31P NMR
(CH2Cl2): s, 14.8 ppm. Compound 5, 31P NMR (CH2Cl2): s, 13.3 ppm.
Supplementary material
CCDC 667634, 667635 and 667636 contain the supplementary
crystallographic data for 3, 4 and 5. These data can be obtained free
of charge via http://www.ccdc.cam.ac.uk/conts/retrieving.html, or
from the Cambridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: (+44) 1223-336-033; or e-mail:
deposit@ccdc.cam.ac.uk.
5. Experimental
All operations were carried out under an argon atmosphere in
dried and degassed solvents using Schlenk techniques. The sol-
vents were thoroughly dried and freshly distilled prior to use.
The IR spectra were run on a Nicolet 510 spectrometer. For the
31P NMR spectra we used the instrument Bruker AC 200. Elemental
analyses were performed by the analytical service of the Fachber-
eich Chemie der Universität Marburg (Germany). Compound 1 was
prepared according to a modified literature procedure [1] by addi-
tion of CS2 to a solution of C(PPh3)2 in toluene at room tempera-
ture. [Cl2Pt(cod)] and [I2Pt(cod)] were obtained according to
literature procedures [18]. Information concerning the X-ray struc-
ture determination is given in Table 1. The residual electron den-
sity in 4 ꢀ 2CH2Cl2 is near the Pt atom.
Acknowledgements
We thank the Deutsche Forschungsgemeinschaft for financial
support. W.P. is also grateful to the Max-Planck-Society, Munich,
Germany, for financial support.
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