Synthesis and characterization of new dimethylplatinum(IV) complexes with o-(diphenylphosphino)thioanisole and its chalcogenide derivatives as ligands. Crystal structure of trans-[Me2PtBr2{ (o-Ph2P(S)C6H4SMe-S,S′})]

Article abstract of DOI:10.1016/S0277-5387(01)00925-1

The compound o-(diphenylphosphino)thioanisole can be oxidized by S or Se in benzene leading to the derivatives Ph₂P(E)C₆H₄SMe [EPSMe; E = S (1), Se (2)]. These compounds act as bidentate chelate ligands in reactions with the platinum(IV) complex [Me₂PtBr₂]_n to form trans and cis isomers of the general formula [Me₂PtBr₂(L₂)] [L₂ = SPSMe (3, 4); SePSMe (5, 6)]. The reaction of the complex [Me₂PtBr₂]_n with the starting ligand Ph₂PC₆H₄SMe (PSMe) led to a reductive elimination affording the neutral complex [PtBr₂(PSMe)] (7). The structure of the complex [Me₂PtBr₂{ (o-Ph₂P(S)C₆H₄SMe})] was established by X-ray crystallography. The platinum atom has a distorted octahedral coordination and it is bonded to two methyl carbons, two bromide atoms and two sulfur atoms of the (o-diphenylphosphinesulfide)thioanisole bidentate ligand.

Full text of DOI:10.1016/S0277-5387(01)00925-1

Polyhedron 20 (2001) 3127–3132
www.elsevier.com/locate/poly
Synthesis and characterization of new dimethylplatinum(IV)
complexes with o-(diphenylphosphino)thioanisole and its
chalcogenide derivatives as ligands. Crystal structure of
trans-[Me2PtBr2{o-Ph2P(S)C6H4SMeꢀS,S%}]
Rau´l Contreras a,*, Mauricio Valderrama a, Cecilia Beroggi a, Daphne Boys b
a Departamento de Qu´ımica Inorga´nica, Facultad de Qu´ımica, Pontificia Uni6ersidad Cato´lica de Chile, Casilla 306, Santiago-22, Chile
b Departamento de F´ısica, Facultad de Ciencias F´ısicas y Matema´ticas, Uni6ersidad de Chile, Casilla 487-3, Santiago, Chile
Received 22 December 2000; accepted 21 August 2001
Abstract
The compound o-(diphenylphosphino)thioanisole can be oxidized by S or Se in benzene leading to the derivatives
Ph2P(E)C6H4SMe [EPSMe; E=S (1), Se (2)]. These compounds act as bidentate chelate ligands in reactions with the platinum(IV)
complex [Me2PtBr2]n to form trans and cis isomers of the general formula [Me2PtBr2(L2)] [L2=SPSMe (3, 4); SePSMe (5, 6)]. The
reaction of the complex [Me2PtBr2]n with the starting ligand Ph2PC6H4SMe (PSMe) led to a reductive elimination affording the
neutral complex [PtBr2(PSMe)] (7). The structure of the complex [Me2PtBr2{o-Ph2P(S)C6H4SMe}] was established by X-ray
crystallography. The platinum atom has a distorted octahedral coordination and it is bonded to two methyl carbons, two bromide
atoms and two sulfur atoms of the (o-diphenylphosphinesulfide)thioanisole bidentate ligand. © 2001 Elsevier Science Ltd. All
rights reserved.
Keywords: Platinum; Phosphino–thioether complexes; Dimethylplatinum(IV) complexes; Reductive elimination reaction; Dichalcogenide com-
plexes
L=glycinate [4–6], glyphosate [7], aspartate [8] and
iminodiacetate [9]. In addition, neutral dimethylplatinu-
m(IV) complexes have been synthesized through an
oxidative addition reaction of dimethylplatinum(II)
complexes containing bidentate N-donor ligands [10–
15].
Thioether ligands have been widely studied as coordi-
nated species in organometallic platinum(IV) com-
pounds. Studies on these types of ligands are quite
ancient and, generally, they have been focalized on
their fluxional property. In particular, there has been
much interest in the inversion of the pyramidal environ-
ment about the sulfur atom [16–18]. On the other
hand, phosphine–thioether ligands can be coordinated
to a metallic center as monodentate P-donor or biden-
tate chelate P,S-donor ligands, behavior which is an
essential condition for the generation of potential cata-
lytic active systems [19,20]. One of the most used phos-
phine–thioether ligands is the o-(diphenylphosphino)-
1. Introduction
A large number of neutral and cationic trimethylplat-
inum(IV) complexes have been prepared from the start-
ing tetranuclear complex [{Me3PtI}4]. In particular,
complexes containing phosphines and pyridines have
attracted special attention because some of them un-
dergo a reductive elimination reaction with the forma-
tion of platinum(II) complexes and ethane [1]. This type
of reaction occurs in dialkylplatinum(IV) derivatives
containing phosphines as ligands [1d,2]. However, the
synthesis of dimethylplatinum(IV) complexes has been
scarce, mainly due to the difficulty in preparing the
precursor compound [Me2PtBr2]n [3]. Some examples of
the reported dimethylplatinum(IV) compounds derived
from this precursor are of the [Me2PtBr2L2] type, where
* Corresponding author. Fax: +56-2-2-6864744.
E-mail address: rcontrer@puc.cl (R. Contreras).
0277-5387/01/$ - see front matter © 2001 Elsevier Science Ltd. All rights reserved.
PII: S0277-5387(01)00925-1

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R. Contreras et al. / Polyhedron 20 (2001) 3127–3132
thioanisole, which usually acts as a bidentate chelate
ligand and has been studied mainly in demethylation or
methyl transfer reactions from the methylthioether
groups [21–23].
2.3. Synthesis of the complexes
2.3.1. trans and cis-[Me2PtBr2(L2)] [L2=SPSMe (3,
4); SePSMe (5, 6)]
In this paper we report the synthesis and characteri-
zation of sulfur and selenium derivatives of o-
(diphenylphosphino)thioanisole, EPSMe (E=S, Se),
and the trans and cis dimethylplatinum(IV) complexes
formed from these ligands. A reductive elimination
reaction was observed in the reaction of [Me2PtBr2-
(THF)x] with o-(diphenylphosphino)thioanisole. The
structure of the complex [Me2PtBr2{o-Ph2P(S)C6H4-
SMe}], determined by single-crystal X-ray diffraction,
is also reported.
To a solution of the complex [Me2PtBr2]n (100 mg;
0.260 mmol) in methanol (30 cm3), a stoichiometric
amount of the corresponding bidentate ligand (SPSMe,
88.5 mg; SePSMe, 100.6 mg), dissolved in chloroform
(10 cm3), was added. The mixture was stirred under
reflux for 3 h and the solution obtained was evaporated
to dryness at reduced pressure. The solid residue was
dissolved in the minimal volume of dichloromethane
and chromatographed on silicagel. The trans-isomer
was isolated using dichloromethane as the eluent while
the cis-isomer was isolated by elution with acetone. The
solutions obtained were concentrated to a small volume
and the complexes precipitated by the addition of di-
ethyl ether or n-hexane. The solids were filtered,
washed with diethyl ether and dried in vacuum. 3: Yield
54 mg (29%). Found: C, 34.4; H, 3.4; S, 8.5. Anal. Calc.
2. Experimental
2.1. Materials and physical measurements
1
for C21H23Br2PPtS2: C, 34.8; H, 3.2; S, 8.8%. H NMR
All reactions were carried out by Schlenk techniques
under a dry nitrogen atmosphere. Reagent grade sol-
vents were dried, distilled and stored under a nitrogen
atmosphere. The starting complexes [Me3PtI]4 [24],
[Me2PtBr2]n [25] and the ligand o-(diphenylphos-
phino)thioanisole [26] were synthesized according to the
literature procedures.
Elemental analyses were carried out with a Perkin–
Elmer 240C microanalyzer. IR spectra were recorded in
a Bruker IFS-25 spectrophotometer using KBr pellets.
1H and 31P{1H} NMR spectra were recorded in a
Bruker AC-200P spectrometer. Chemical shifts are re-
ported in parts per million relative to Me4Si (1H) and
85% H3PO4 (31P{1H}, positive shifts downfield) as in-
ternal and external standards, respectively.
(CDCl3): l 1.99 [s, 3H, 2J(PtH)=72.0 Hz, PtꢀMe
2
(trans to SMe)], 2.38 [s, 3H, J(PtH)=73.5 Hz, PtꢀMe
3
(trans to SPPh2)], 2.57 [s, 3H, SMe, J(PtH)=10.9 Hz].
2
31P{1H} NMR (CDCl3): l 36.2 [s, J(PtP)=43.7 Hz].
4: Yield 49 mg (26%). Found: C, 34.5; H, 3.3; S, 8.4.
Anal. Calc. for C21H23Br2PPtS2: C, 34.8; H, 3.2; S,
1
2
8.8%. H NMR (CDCl3): l 0.64 [s, 3H, J(PtH)=72.5
2
Hz, PtꢀMe (trans to Br)], 1.24 [s, 3H, J(PtH)=72.4
Hz, PtꢀMe (trans to SMe)], 2.57 [s, 3H, SMe,
3J(PtH)=11.6 Hz]. 31P{1H} NMR (CDCl3): l 35.6 [s,
2J(PtP)=46.2 Hz]. 5: Yield 61 mg (30%). Found: C,
32.9; H, 3.1; S, 3.9. Anal. Calc. for C21H23Br2PPtSSe: C,
1
32.7; H, 3.0; S, 4.2%. H NMR (CDCl3): l 2.01 [s, 3H,
2J(PtH)=71.0 Hz, PtꢀMe (trans to SMe)], 2.32 [s, 3H,
2J(PtH)=73.3 Hz, PtꢀMe (trans to SePPh2)], 2.58 [s,
3
3H, SMe, J(PtH)=11.0 Hz,]. 31P{1H} NMR (CDCl3):
l 23.0 [s, 2J(PtP)=44.0 Hz, 1J(PSe)=628 Hz]. 6: Yield
74 mg (37%). Found: C, 32.5; H, 2.8; S, 4.0. Anal. Calc.
for C21H23Br2PPtSSe: C, 32.7; H, 3.0; S, 4.2%. 1H
NMR (CDCl3): l 0.65 [s, 3H, 2J(PtH)=72.8 Hz,
2.2. Synthesis of the ligands
2.2.1. o-Ph2P(E)C6H4SMe [E=S(1), Se(2)]
To a solution of o-(diphenylphosphino)thioanisole
(1.5 g; 4.4 mmol) in benzene (150 cm3), an excess
amount of the element E [4.8 mmol; E=S (0.156 g); Se
(0.385 g)] was added. The resulting mixture was stirred
under reflux for 2 h. The solution obtained was concen-
trated to a small volume and the compounds precipi-
tated as pale-yellow solids by the addition of n-hexane.
The ligands were filtered, washed with carbon disulfide
and diethyl ether, and dried in vacuum. 1: Yield 1.24 g
(75%). Found: C, 67.0; H, 3.4; S, 18.3. Anal. Calc. for
C19H17PS2: C, 67.0; H, 3.9; S, 18.8%. 1H NMR
(CDCl3): l 2.32 (s, 3H, SMe). 31P{1H} NMR (CDCl3):
l 40.6 (s). 2: Yield 1.88 g (99%). Found: C, 59.1; H, 3.8;
S, 8.1. Anal. Calc. for C19H17PSSe: C, 58.9; H, 3.4; S,
18.3%. 1H NMR (CDCl3): l 2.33 (s, 3H, SMe). 31P{1H}
2
PtꢀMe (trans to Br)], 1.26 [s, 3H, J(PtH)=71.6 Hz,
3
PtꢀMe (trans to SMe)], 2.57 [s, 3H, SMe, J(PtH)=
2
11.5 Hz,]. 31P{1H} NMR (CDCl3): l 21.9 [s, J(PtP)=
1
46.0 Hz, J(PSe)=630 Hz].
2.3.2. [PtBr2(PSMe)] (7)
The complex was prepared by the two following
methods. (i) To a solution of the complex [Me2PtBr2]n
(100 mg; 0.260 mmol), in a mixture of methanol–chlo-
roform (30–10 cm3), a stoichiometric amount of the
PSMe (80 mg, 0.26 mmol) was added. The mixture was
stirred under reflux for 3 h. The solution obtained was
evaporated to dryness at reduced pressure and the solid
residue extracted with dichloromethane. The complex,
precipitated as a yellow solid by the addition of diethyl
1
NMR (CDCl3): l 31.1 [t, J(PSe)=730 Hz].

R. Contreras et al. / Polyhedron 20 (2001) 3127–3132
3129
ether, was filtered, washed with diethyl ether or n-hex-
ane, and dried in vacuum. Yield 90 mg (52%). Found:
C, 34.5; H, 2.3; S, 4.7. Anal. Calc. for C19H17Br2PPtS:
C, 34.4; H, 2.6; S, 4.8%. (ii) To a solution of the
complex K2PtBr4 (200 mg; 0.337 mmol) in methanol
(30 cm3) a stoichiometric amount of PSMe (199.8 mg;
0.337 mmol) in chloroform (10 cm3) was added. The
mixture was stirred for 1 h, the solution evaporated to
dryness at reduced pressure and the solid residue ex-
tracted with chloroform. The addition of n-hexane led
to the precipitation of a solid, which was filtered,
washed with diethyl ether and dried in vacuum. Yield
202 mg (90%). Found: C, 34.3; H, 2.4; S, 4.6%. 1H
NMR (CDCl3): l 3.15 [s, 3H, 3J(PtH)=45.0 Hz, SMe].
1
31P{1H} NMR (CDCl3): l 37.2 [s, J(PtP)=3498 Hz].
2.4. X-ray crystal structure determination for
trans-[Me2PtBr2(SPSMe)] (3)
Table 1
Crystal data and structure refinement parameters for complex 3
Empirical formula
Formula weight
Temperature (K)
Crystal system
Space group
Unit cell dimensions
C
21H23Br2PPtS2
Suitable crystals for X-ray diffraction determination
were obtained from a slow diffusion of diethyl ether
into a solution of complex 3 in dichloromethane. Inten-
sity data were collected at room temperature (r.t.) on a
Siemens R3m/V diffractometer with graphite
725.39
293(2)
triclinic
(
P1
,
,
a (A)
8.764(1)
11.301(2)
12.669(3)
74.76(2)
85.12(2)
83.17(2)
1200.1(4)
2
monochromated Mo Ka radiation (u=0.71073 A) by
,
b (A)
the q–2q scan method. Semiempirical corrections based
on „ scans were applied for absorption. The structure
was solved by direct methods and refined on F2 by
full-matrix least-squares calculations with SHELXL-97
[27]. A riding model was applied to the H atoms, and
,
c (A)
h (°)
i (°)
k (°)
V (A )
3
,
Z
,
placed at calculated positions with CꢀH=0.96 A. Rele-
vant crystal data and refinement parameters are sum-
Dcalc (Mg m−3
)
2.007
9.420
Absorption coefficient (mm−1
Crystal size (mm)
q Range (°)
)
marized in Table 1.
0.44×0.26×0.14
1.67–27.56
05h511, −145k514,
−165l516
5876
5518 [Rint=0.0173]
244
1.035
Index ranges
3. Results and discussion
Reflections collected
Independent reflections
Parameters refined
The
bidentate
ligand
o-(diphenylphosphino)-
Goodness-of-fit on F2
Final R indices [I\2|(I)] a
R indices (all data) b
thioanisole (o-Ph2PC6H4SMe, PSMe] reacts with ele-
mental sulfur or selenium by the oxidation of the
phosphorus atom to give the corresponding chalco-
genide derivatives of the type Ph2P(E)C6H4SMe
(EPSMe, E=S or Se) (1).
R1=0.039, wR2=0.099
R1=0.051, wR2=0.104
1.341 and −1.901
Largest difference peak and hole
(e A
−3
,
)
a R1 (F)=ꢀꢁ ꢁFoꢁ−ꢁFcꢁ ꢁ/ꢀꢁFoꢁ.
b wR2
(F2)=[ꢀ[w(Fo2−Fc2)2]/ꢀ{w(Fo2)2}]1/2
;
where
w=(1/
[|2(Fo2)+0.0678P]) and P=(Fo2+2Fc2)/3.
(1)
These compounds were characterized by elemental
analyses and NMR (1H and 31P{1H}) spectroscopy.
1
The H NMR spectra of ligands 1 and 2 exhibited a
singlet resonance at l 2.32 and 2.33 ppm, respectively,
assigned to the methylthioether group [28]. The 31P{1H}
NMR spectra of the ligands 1 and 2 showed a singlet
signal at l 40.6 and 31.1 ppm [1J(PSe)=730 Hz],
respectively.
The reaction of the bidentate ligands EPSMe (E=S
or Se) with the solvated platinum(IV) complex
[Me2PtBr2(MeOH)x] (formed by dissolving the polymer
[Me2PtBr2]n in methanol), in a mixture of methanol–
chloroform at room temperature, afforded the forma-
tion of trans- and cis-isomer complexes of the general
formula [Me2PtBr2(EPSMe)] (E=S or Se) (Scheme 1).
Scheme 1.

3130
R. Contreras et al. / Polyhedron 20 (2001) 3127–3132
Table 2
NMR a chemical shifts (l) and coupling constants (Hz) for the platinum(IV) complexes (3–6)
Complex
lH
lP
PtꢀMe
2J(PtꢀH)
trans Atom
Sme
3J(PtꢀH)
10.9
P
2J(PtꢀP)
3
1.99(s)
2.38(s)
0.64(s)
1.24(s)
2.01(s)
2.32(s)
0.65(s)
1.26(s)
72.0
73.5
72.5
72.4
71.0
73.3
72.8
71.6
SMe
S
Br
SMe
SMe
Se
2.57(s)
2.57(s)
2.58(s)
2.57(s)
36.2(s)
35.6(s)
23.0(s)
21.0(s)
44
46
44
46
4
11.6
5 b
6 c
11.0
Br
SMe
11.5
a Measured in CDCl3 at room temperature. Chemical shifts relative to SiMe4 and 85% H3PO4 as standards. All complexes show multiplets in
the region l 6.8–7.9 ppm corresponding to the phenyl groups of the ligands.
b 1J(PSe)=628 Hz.
c 1J(PSe)=630 Hz.
Relevant NMR chemical shifts and coupling con-
stants are summarized in Table 2. The 1H NMR spectra
of complexes 3–6 show, in the methyl–platinum region,
two singlet resonances in a 1:1 intensity ratio with the
corresponding satellites due to 195PtꢀH coupling. The
methyl–platinum resonances at the trans position of the
SMe, Br or EP groups are assigned on the basis of the
2J(PtꢀH) coupling values [15,29–31]. In addition, all the
1H NMR spectra show a singlet resonance at l 2.57
ppm [3J(PtꢀH)=10.9–11.5 Hz] attributed to the
methylthioether protons. The 31P{1H} NMR spectra of
complexes 3–6 show a singlet signal in the range l
3 with atom labeling is shown in Fig. 1. Relevant bond
lengths and bond angles are given in Table 3. The
platinum atom shows a distorted octahedral coordina-
tion and is bonded to two methyl carbons, two bromide
atoms and two-sulfur atoms of the (o-diphenylphosphi-
nesulfide)thioanisole bidentate ligand.
The PtꢀC(Me) bond lengths [PtꢀC(1)=2.106(5) and
,
PtꢀC(2)=2.065(6) A] are similar to those found in the
related dimethyl–platinum(IV) complexes [Me2PtI2-
,
{(pz)2(thi)CH}] [PtꢀC: 2.070(7) and 2.097(9) A] [11] and
5
,
[(h -C5Me5)Ir(m-pz)3PtMe3] [2.079(9) and 2.059(12) A]
,
[36]. The PtꢀBr bond lengths [2.447(1) and 2.460(1) A]
2
are comparable to the terminal PtꢀBr distances in com-
21.0–36.2 ppm with a coupling of J(PtP)=44–46 Hz
5
,
plexes [Pt(en)Br4] [2.480 A] [37], [(h -C5Me5)PtMe2Br]
[32,33]. The spectra of complexes 5 and 6 present,
moreover, the corresponding 1J(PꢀSe) coupling with
values of 628 and 630 Hz, respectively [34].
Interestingly, the treatment of complex [Me2PtBr2]n
with the precursor ligand (PSMe) in methanol solution
at room temperature led to a reductive elimination
reaction yielding the neutral complex [PtBr2(PSMe)] (7)
and ethane (Eq. (2)).
5
,
[2.498(2) A] [38] and [(h -C5Me5)PtMeBr2] [2.462(2) and
,
2.496(2) A] [38], but shorter than the bridging PtꢀBr
,
distance in [(Me3PtBr)4]·0.5 toluene [2.677(3) A] [39].
,
The PtꢀS(2) distance [2.515(2) A] is slightly larger
than PtꢀS(2) [2.501(2) A] implying a greater strength of
the PtꢀC(1) bond compared with PtꢀC(2). According of
the trans influence arguments, the PtꢀC(1) will be larger
,
1/n[Me2PtBr2]n+PSMe“[PtBr2(PSMe)]+C2H6
(2)
As expected, complex 7 can be prepared alternatively
by the reaction of the salt K2PtCl4 with the precursor
ligand (PSMe) in a mixture of methanol–chloroform at
room temperature. Its 1H NMR spectrum shows a
singlet signal at l 3.15 [3J(PtH)=45 Hz] assigned to the
protons of the methyl–thioether group. The 31P{1H}
NMR spectrum exhibited a singlet resonance at l 37.2
[1J(PtP)=3498 Hz]. The magnitude of the coupling
constant is typical of a phosphorus atom trans to a
bromide ligand in platinum(II) complexes [35].
3.1. Crystal structure of complex
[Me2PtBr2{Ph2P(S)C6H4SMe}] (3)
Fig. 1. ORTEP view of the structure of the complex cation 3 with atom
A perspective ORTEP view of the structure of complex
numbering scheme (thermal ellipsoids at 50% probability level).

R. Contreras et al. / Polyhedron 20 (2001) 3127–3132
3131
Table 3
References
,
Selected bond lengths (A) and bond angles (°) for complex 3
[1] (a) D.M. Crumpton, K.I. Goldberg, J. Am. Chem. Soc. 122
(2000) 962;
Bond lengths
PtꢀC(1)
PtꢀBr(1)
PtꢀS(1)
S(1)ꢀP(1)
S(2)ꢀC(4)
P(1)ꢀC(11)
2.106(5)
2.4474(9)
2.501(2)
1.986(2)
1.801(6)
1.797(6)
PtꢀC(2)
PtꢀBr(2)
PtꢀS(2)
S(2)ꢀC(36)
P(1)ꢀC(21)
P(1)ꢀC(31)
2.065(6)
2.4597(10)
2.515(2)
1.780(6)
1.793(5)
1.818(5)
(b) K.I. Goldberg, J.Y. Yan, E.M. Breitung, J. Am. Chem. Soc.
117 (1995) 6889;
(c) M.P. Brown, R.J. Puddephatt, C.E.E. Upton, J. Chem. Soc.,
Dalton Trans. (1974) 2457;
(d) M.P. Brown, R.J. Puddephatt, C.E.E. Upton, S.W. Laving-
ton, J. Chem. Soc., Dalton Trans. (1974) 1613;
(e) H.C. Clark, L.E. Manzer, Inorg. Chem. 12 (1973) 362.
[2] M.W. Holtcamp, J.A. Labinger, J.E. Bercaw, J. Am. Chem. Soc.
119 (1997) 848.
[3] (a) H.C. Clark, L.E. Manzer, Inorg. Chem. 11 (1972) 2749;
(b) J.R. Hall, G.A. Swile, J. Organomet. Chem. 139 (1977) 403.
[4] N.H. Agnew, T.G. Appleton, J.R. Hall, Inorg. Chim. Acta 41
(1980) 71.
[5] T.G. Appleton, J.R. Hall, N.S. Ham, F.W. Hess, M.A. Williams,
Aust. J. Chem. 36 (1983) 673.
[6] N.H. Agnew, T.G. Appleton, J.R. Hall, Inorg. Chim. Acta 41
(1980) 85.
Bond angles
C(1)ꢀPtꢀC(2)
C(1)ꢀPtꢀBr(1)
C(1)ꢀPtꢀBr(2)
C(2)ꢀPtꢀS(1)
Br(1)ꢀPtꢀS(1)
C(2)ꢀPtꢀS(2)
Br(1)ꢀPtꢀS(2)
S(1)ꢀPtꢀS(2)
C(36)ꢀS(2)ꢀC(4)
C(4)ꢀS(2)ꢀPt
86.6(3)
88.0(2)
88.7(2)
C(2)ꢀPtꢀBr(1)
C(2)ꢀPtꢀBr(2)
Br(1)ꢀPtꢀBr(2)
C(1)ꢀPtꢀS(1)
Br(2)ꢀPtꢀS(1)
C(1)ꢀPtꢀS(2)
Br(2)ꢀPtꢀS(2)
P(1)ꢀS(1)ꢀPt
C(36)ꢀS(2)ꢀPt
90.1(2)
89.1(2)
176.65(3)
172.2(2)
91.08(5)
95.8(2)
89.91(5)
107.28(7)
106.4(2)
85.6(2)
92.09(5)
177.4(2)
91.06(4)
91.94(5)
103.1(3)
107.4(3)
C(21)ꢀP(1)ꢀC(11) 106.2(3)
C(11)ꢀP(1)ꢀC(31) 106.7(2)
C(11)ꢀP(1)ꢀS(1)
C(21)ꢀP(1)ꢀC(31) 108.9(2)
C(21)ꢀP(1)ꢀS(1)
C(31)ꢀP(1)ꢀS(1)
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than PtꢀC(2), as in fact occurs in this case, and this is
reflected in the NMR coupling constants, where the
value for the Me(C1) group [2J(PtH)=72.0 Hz] is
smaller than that for the Me(C2) group [2J(PtH)=73.5
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5
,
{(MeS)4(CH)2}] [average: 2.433(7) A] [40] and [(h -
2
,
C5Me5)IrCl{h -Ph2PCH2SPh}]BF4·Me2CO [2.402(3) A]
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5
(S)But2}]ClO4 [2.282(2) A] [32] and [(h -C5Me5)Ir-
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,
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4. Supplementary material
Crystallographic data for structural analysis have
been deposited with the Cambridge Crystallographic
Data Centre, CCDC No. 154567. Copies of this infor-
mation may be obtained free of charge from The
Director, CCDC, 12 Union Road, Cambridge, CB2
1EZ, UK (fax: +44-1223-336033; e-mail: deposit@
ccdc.cam.ac.uk or www: http://www.ccdc.cam.ac.uk).
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