Group 10 derivatives of the silylated sterically hindered aromatic thiolates [C6H4SH-2-SiPh3] and [C6H4SH-2-SiCH3Ph2].

Article abstract of DOI:10.1016/j.ica.2006.05.018

The reactivity of the silylated sterically hindered thiolates [C₆H₄SH-2-SiPh₃] and [C₆H₄SH-2-SiCH₃Ph₂] has been examined with transition metal complexes of group 10. A series of palladium(II) and platinum(II) complexes were obtained. Analysis of these complexes by different spectroscopic techniques and single crystal X-ray diffraction studies revealed the formulations to be dependent of the stoichiometry and relative size of the metal center and thiolate. Analogous reactions with nickel complexes afforded oxidation decomposition products.

Full text of DOI:10.1016/j.ica.2006.05.018

Inorganica Chimica Acta 359 (2006) 4007–4018
www.elsevier.com/locate/ica
Group 10 derivatives of the silylated sterically hindered aromatic
thiolates [C6H4SH-2-SiPh3] and [C6H4SH-2-SiCH3Ph2]. The
crystal structures of trans-[Pd(PPh3)2(SC6H4-2-SiPh3)2],
z-[Pt(PPh3)2(Cl)(SC6H4-2-SiPh3)], e-[Pt(PPh3)2(Cl)-
(SC6H4-2-SiCH3Ph2)], cis-[Pt(PPh3)2(SC6H4-2-SiCH3Ph2)2],
trans-[Pt(PPh3)2(SC6H4-2-SiCH3Ph2)2]
´
´
´
´
Viviana Cordero-Pensado, Valente Gomez-Benıtez, Simon Hernandez-Ortega
*
´
Ruben A. Toscano, David Morales-Morales
Instituto de Quı´mica, Universidad Nacional Auto´noma de Me´xico, Cd. Universitaria, Circuito Exterior, Coyoaca´n, 04510 Me´xico D.F., Mexico
Received 24 February 2006; received in revised form 10 May 2006; accepted 13 May 2006
Available online 24 May 2006
Abstract
The reactivity of the silylated sterically hindered thiolates [C6H4SH-2-SiPh3] and [C6H4SH-2-SiCH3Ph2] has been examined with tran-
sition metal complexes of group 10. A series of palladium(II) and platinum(II) complexes were obtained. Analysis of these complexes by
different spectroscopic techniques and single crystal X-ray diffraction studies revealed the formulations to be dependent of the stoichi-
ometry and relative size of the metal center and thiolate. Analogous reactions with nickel complexes afforded oxidation decomposition
products.
ꢀ 2006 Elsevier B.V. All rights reserved.
Keywords: Sterically hindered thiols; Thiolate complexes; Palladium complexes; Crystal structures
1. Introduction
thiolate complexes continue to attract considerable interest
due to the aforementioned chemical properties and struc-
tural diversity [3].
The interesting properties that sterically hindered thiols
confer to the compounds they form with transition metal
complexes have been known for a number of years. Thus,
some of these ligands have been employed for the synthesis
of species with unusual structures and reactivities [1]. Of
fundamental importance has been the use of thiols as
ligands for the synthesis of different compounds for the
modeling of active centers of metalloenzymes, this being
particularly true in the case of the nitrogenase [2]. Hence,
Given the facility with which thiols can be tuned both
sterically and electronically, they have been widely used
as auxiliary ligands. The presence of electron-withdrawing
groups or substituents with steric requirements favors the
formation of mononuclear complexes rather than the thio-
late bridged oligomers, usually generated by using unen-
cumbered thiols [1]. Moreover, thiolate complexes are
known to undergo chemistry at the sulfur center, including
redox and protonation–deprotonation processes, which is a
plus to traditional chemistry as these complexes are usually
centered on the metal [4]. Thus, following our current inter-
est in the synthesis, structural studies and applications of
*
Corresponding author. Tel.: +52 55 56224514; fax: +52 55 56162217.
E-mail address: damor@servidor.unam.mx (D. Morales-Morales).
0020-1693/$ - see front matter ꢀ 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2006.05.018

4008
V. Cordero-Pensado et al. / Inorganica Chimica Acta 359 (2006) 4007–4018
2.2. Synthesis of trans-[Pd(PPh3)2(SC6H4-2-SiPh3)2] (1)
To a CH2Cl2 solution (10 mL) of trans-[PdCl2(PPh3)2]
(51.4 mg, 0.073 mmol), a solution consisting of [C6H4SH-
2-SiPh3] (54 mg, 0.146 mmol) and NEt3 (0.23 mL,
0.146 mmol) in 10 mL of CH2Cl2 was added dropwise
under stirring. The resulting reaction mixture was allowed
to stir overnight. After this time, the reaction was filtered
off and the solvent evaporated under vacuum, to afford a
microcrystalline red-orange powder. Yield: 63%. M.p.
Si
Si
SH
Me
SH
Scheme 1. Structure of the silylated sterically hindered thiols [C6H4SH-2-
SiPh3] and [C6H4SH-2-SiCH3Ph2].
1
148–150 ꢁC. H NMR (300 MHz, CDCl3), d 7.6–6.9 (m,
Ph, 68H); 31P{1H} NMR (121 MHz, CDCl3), d 24.6 (s,
P). Elem. Anal. Calc. for [C84H68P2PdS2Si2]: C, 73.85; H,
5.02. Found: C, 73.49; H, 5.04%. MS-FAB+ [MÀ(PPh3-
SC6H4-2-SiPh3)+] = 735 m/z.
thiolate complexes in industrial relevant catalytic transfor-
mations [5], we would like to report our findings on the
reactivity of transition metal complexes of group 10 and
the silylated sterically hindered thiols [C6H4SH-2-SiPh3]
and [C6H4SH-2-SiCH3Ph2] (Scheme 1).
2.3. Synthesis of trans-[Pd(PPh3)2(SC6H4-2-SiCH3Ph2)2]
(2)
2. Experimental
To a CH2Cl2 solution (10 mL) of trans-[PdCl2(PPh3)2]
(51.4 mg, 0.073 mmol), a solution consisting of [C6H4SH-
2-(SiCH3Ph2)] (54 mg, 0.146 mmol) and NEt3 (0.23 mL,
0.146 mmol) in 10 mL of CH2Cl2 was added dropwise
under stirring. A microcrystalline, brown-reddish powder
was formed. Yield: 53%. M.p. 152 ꢁC. 1H NMR
(300 MHz, CDCl3), d 7.4–7.0 (m, Ph, 58H), 2.17 (s, Me,
6H); 31P{1H} NMR (121 MHz, CDCl3), d 29.3 (s, P).
Elem. Anal. Calc. for [C74H64P2PdS2Si2]: C, 71.56; H,
5.19. Found: C, 71.89; H, 5.21%. MS-FAB+ [MÀ(PPh3-
SC6H4-2-SiMePh2)+] = 673 m/z.
2.1. General
Unless stated otherwise, all reactions were carried out
under an atmosphere of dinitrogen using conventional
Schlenk glassware and the solvents were dried using estab-
lished procedures and distilled under dinitrogen immedi-
ately prior to use. The IR spectra were recorded on a
Nicolet-Magna 750 FT-IR spectrometer as nujol mulls.
The 1H NMR (300 MHz) spectra were recorded on a JEOL
GX300 spectrometer. Chemical shifts are reported in ppm
downfield of TMS using the solvent (CDCl3, d = 7.27) as
an internal standard. 31P{1H} NMR (121 MHz) spectra
were recorded with complete proton decoupling and are
reported in ppm using 85% H3PO4 as external standard.
Elemental analyses were determined on a Perkin–Elmer
240. Positive-ion FAB mass spectra were recorded on a
JEOL JMS-SX102A mass spectrometer operated at an
accelerating voltage of 10 kV. The samples were desorbed
from a nitrobenzyl alcohol (NOBA) matrix using 3 keV
xenon atoms. Mass measurements in FAB are performed
at a resolution of 3000 using magnetic field scans and the
matrix ions as the reference material or, alternatively, by
electric field scans with the sample peak bracketed by two
(polyethylene glycol or cesium iodide) reference ions. Melt-
ing points were determined in a MEL-TEMP capillary
melting point apparatus and are reported without
correction.
2.4. Synthesis of z-[Pt(PPh3)2(Cl)(SC6H4-2-SiPh3)] (3)
To a CH2Cl2 solution (20 mL) of cis-[PtCl2(PPh3)2]
(52.3 mg, 0.066 mmol), a solution consisting of [C6H4SH-
2-(SiPh3)] (25 mg, 0.066 mmol) and NEt3 (0.12 mL,
0.74 mmol) in 10 mL of CH2Cl2 was added dropwise under
stirring. The resulting reaction mixture was allowed to stir
overnight. After this time, the reaction was filtered off and
the solvent evaporated under vacuum, to afford a micro-
crystalline yellow powder. Yield: 86%. M.p. 203 ꢁC. 1H
NMR (300 MHz, CDCl3), d 7.8–6.9 (m, Ph, 49H);
31P{1H} NMR (121 MHz, CDCl3), d 20.7 (s, JP–Pt
=
1.47 kHz, 1P-e configuration). Elem. Anal. Calc. for
[C60H49ClP2PtSSi]: C, 64.19; H, 4.40. Found: C, 62.58;
H, 4.30%. MS-FAB+ [M+] = 1122 m/z.
2.5. Synthesis of cis-[Pt(PPh3)2(SC6H4-2-SiPh3)2] (4)
and trans-[Pt(PPh3)2(SC6H4-2-SiPh3)2] (5)
The PdCl2, PtCl2 and NiCl2 were obtained commercially
from Aldrich Chem. Co. Compounds trans-[NiCl2(PPh3)2]
[6], trans-[PdCl2(PPh3)2] [7], cis-[PtCl2(PPh3)2] [8],
[C6H4SH-2-SiPh3] and [C6H4SH-2-SiCH3Ph2] [9] were syn-
thesized according to the published procedures.
All palladium and platinum complexes were synthesized
in an analogous manner according to the following proce-
dure described for the synthesis of complex trans-
[Pd(PPh3)2(SC6H4-2-SiPh3)2] (1).
To a CH2Cl2 solution (20 mL) of cis-[PtCl2(PPh3)2]
(52.3 mg, 0.066 mmol), a solution consisting of [C6H4SH-
2-(SiPh3)] (49 mg, 0.132 mmol) and NEt3 (0.23 mL,
0.146 mmol) in 10 mL of CH2Cl2 was added dropwise
under stirring. The resulting reaction mixture was allowed
to stir overnight. After this time, the reaction was filtered
off and the solvent evaporated under vacuum, to afford a

Table 1
Summary of crystal structure data for trans-[Pd(PPh3)2(SC6H4-2-SiPh3)2] (1), z-[Pt(PPh3)2(Cl)(SC6H4-2-SiPh3)] (3), e-[Pt(PPh3)2(Cl)(SC6H4-2-SiCH3Ph2)] (6), cis-[Pt(PPh3)2(SC6H4-2-SiCH3Ph2)2] (7),
and trans-[Pt(PPh3)2(SC6H4-2-SiCH3Ph2)2] (8)
Compound
trans-[Pd(PPh3)2-
z-[Pt(PPh3)2-(Cl)-
e-[Pt(PPh3)2(Cl)-
cis-[Pt(PPh3)2-
trans-[Pt(PPh3)2-
(SC6H4-2-SiPh3)2] (1)
(SC6H4-2-SiPh3)] (3)
(SC6H4-2-SiCH3Ph2)] (6)
(SC6H4-2-SiCH3Ph2)2] (7)
(SC6H4-2-SiCH3Ph2)2] (8)
Empirical formula
Formula weight
Temperature (K)
Crystal system
C
84H68P2PdS2Si2
C60H49ClP2PtSSi
1122.62
293(2)
C56H49Cl3P2PtSSi
1145.48
291(2)
C74.50H65ClP2PtS2Si2
1373.04
293(2)
C74.50H65ClP2PtS2Si2
1373.04
293(2)
1366.02
293(2)
monoclinic
C2
triclinic
triclinic
triclinic
triclinic
ꢀ
ꢀ
ꢀ
ꢀ
Space group
P1
P1
P1
P1
Crystal size (mm)
Unit cell dimensions
0.20 · 0.13 · 0.10
0.298 · 0.240 · 0.134
0.32 · 0.24 · 0.12
0.298 · 0.126 · 0.074
0.254 · 0.180 · 0.162
˚
a (A)
26.301(2)
11.522(1)
13.048(1)
90
119.115(1)
90
3454.4(5)
2
1.313
11.666(1)
20.637(1)
22.394(1)
84.186(1)
76.730(1)
74.131(1)
5043.2(5)
4
12.9001(7)
13.9902(8)
16.2602(9)
82.921(1)
84.281(1)
63.133(1)
2594.6(2)
2
13.768(1)
14.864(1)
19.576(1)
68.566(1)
83.247(1)
64.503(1)
3362.2(4)
2
14.145(1)
14.225(1)
18.587(1)
72.397(1)
72.273(1)
75.303(1)
3341.3(4)
2
˚
b (A)
˚
c (A)
a (ꢁ)
b (ꢁ)
c (ꢁ)
3
˚
V (A )
Z
Dcalc (g/cm3)
1.479
1.446
1.356
1.365
h Range for data collection (ꢁ)
Reflections collected
1.79–25.00
14315
1.86–25.02
60098
1.77–25.00
21456
1.76–25.01
40097
1.19–25.02
36821
Independent reflections (Rint
F(000)
)
6076 (0.0552)
1416
17749 (0.0523)
2256
9138 (0.0328)
1148
11829 (0.0798)
1394
11785 (0.0439)
1394
Absorption correction
analytical
0.360 and À0.462
analytical
1.654 and À0.944
analytical
1.149 and À0.788
analytical
1.710 and À0.605
analytical
2.195 and À0.796
Final maximum and minimum of
difference electron density map
Goodness-of-fit on F2
0.935
0.931
0.928
1.002
1.049
R indices (all data)
R1 = 0.0619, wR2 = 0.0534
R1 = 0.0422, wR2 = 0.0500
6076/1/411
R1 = 0.0624, wR2 = 0.0554
R1 = 0.0389, wR2 = 0.0521
17749/0/1189
R1 = 0.0369, wR2 = 0.0642
R1 = 0.0310,wR2 = 0.0631
9138/2/580
R1 = 0.0630, wR2 = 0.1310
R1 = 0.0490, wR2 = 0.1253
11829/0/749
R1 = 0.0561, wR2 = 0.1325
R1 = 0.0451, wR2 = 0.1267
11785/0/737
Final R indices [I > 2r(I)]
Data/restraints/parameters
Index ranges
À31 6 k 6 31, À13 6 h 6 13,
À13 6 k 6 13, À23 6 h 6 24,
À15 6 k 6 15, À16 6 h 6 16,
À16 6 k 6 16, À17 6 h 6 17,
À16 6 k 6 16, À16 6 h 6 16,
À15 6 l 6 15
À26 6 l 6 26
À19 6 l 6 19
À23 6 l 6 23
À22 6 l 6 22

Table 2
˚
Selected bond lengths (A) and angles (ꢁ) for trans-[Pd(PPh3)2(SC6H4-2-SiPh3)2] (1), z-[Pt(PPh3)2(Cl)(SC6H4-2-SiPh3)] (3), e-[Pt(PPh3)2(Cl)(SC6H4-2-SiCH3Ph2)] (6), cis-[Pt(PPh3)2(SC6H4-2-SiCH3Ph2)2]
(7), and trans-[Pt(PPh3)2(SC6H4-2-SiCH3Ph2)2] (8)
trans-[Pd(PPh3)2(SC6H4-2-SiPh3)2]
(1)a
z-[Pt(PPh3)2(Cl)(SC6H4-2-SiPh3)]
(3)
e-[Pt(PPh3)2(Cl)(SC6H4-2-
SiCH3Ph2)] (6)
cis-[Pt(PPh3)2(SC6H4-2-
SiCH3Ph2)2] (7)
trans-[Pt(PPh3)2(SC6H4-2-
SiCH3Ph2)2] (8)
˚
Bond lengths (A)
Pd(1)–S(1)
Pd(1)–S(1)b
Pd(1)–P(1)b
Pd(1)–P(1)
Si(1)–C(7)
Si(1)–C(2)
Si(1)–C(19)
Si(1)–C(13)
2.3293(9)
2.3293(9)
2.3523(10)
2.3523(10)
1.881(4)
1.827(4)
1.871(4)
1.872(5)
Pt(1)–P(2)
Pt(1)–P(1)
Pt(1)–S(1)
Pt(1)–Cl(1)
Si(1)–C(7)
Si(1)–C(2)
Si(1)–C(19)
Si(1)–C(13)
2.2477(14)
Pt(1)–P(2)
Pt(1)–P(1)
Pt(1)–S(1)
Pt(1)–Cl(1)
Si(1)–C(7)
Si(1)–C(2)
Si(1)–C(19)
Si(1)–C(13)
2.3192(10)
Pt(1)–P(2)
Pt(1)–P(1)
Pt(1)–S(1)
Pt(1)–S(2)
Si(1)–C(27)
Si(1)–C(26)
Si(1)–C(33)
Si(1)–C(21)
Si(2)–C(7)
Si(2)–C(2)
Si(2)–C(14)
Si(2)–C(8)
2.2813(18)
2.2884(18)
2.3476(17)
2.3723(17)
1.858(8)
1.866(8)
1.880(8)
1.885(7)
1.860(8)
1.872(7)
1.875(7)
1.899(8)
Pt(1)–P(2)
Pt(1)–P(1)
Pt(1)–S(1)
Pt(1)–S(2)
Si(1)–C(7)
Si(1)–C(14)
Si(1)–C(2)
Si(1)–C(8)
Si(2)–C(33)
Si(2)–C(26)
Si(2)–C(21)
Si(2)–C(27)
2.3080(18)
2.2954(13)
2.3344(13)
2.3515(13)
1.855(5)
1.874(5)
1.879(5)
2.3061(10)
2.3061(9)
2.3401(9)
1.888(4)
1.883(4)
1.858(4)
1.870(4)
2.3052(17)
2.3402(16)
2.3275(16)
1.871(7)
1.875(8)
1.877(6)
1.884(7)
1.858(8)
1.858(7)
1.878(7)
1.880(7)
1.888(5)
Bond angles (ꢁ)
S(1)–Pd(1)–S(1)b
S(1)–Pd(1)–P(1)b
S(1)b–Pd(1)–P(1)b
S(1)–Pd(1)–P(1)
S(1)b–Pd(1)–P(1)
P(1)b–Pd(1)–P(1)
C(19)–Si(1)–C(13)
C(19)–Si(1)–C(2)
C(13)–Si(1)–C(2)
C(19)–Si(1)–C(7)
C(13)–Si(1)–C(7)
C(2)–Si(1)–C(7)
169.48(7)
96.11(3)
82.72(3)
82.72(3)
96.11(3)
167.31(7)
111.0(2)
108.71(19)
113.79(19)
105.26(17)
108.0(2)
P(2)–Pt(1)–P(1)
P(2)–Pt(1)–S(1)
P(1)–Pt(1)–S(1)
P(2)–Pt(1)–Cl(1)
P(1)–Pt(1)–Cl(1)
S(1)–Pt(1)–Cl(1)
C(7)–Si(1)–C(2)
C(7)–Si(1)–C(19)
C(2)–Si(1)–C(19)
C(7)–Si(1)–C(13)
C(2)–Si(1)–C(13)
C(19)–Si(1)–C(13)
97.93(5)
87.12(5)
172.31(5)
176.29(5)
82.89(5)
92.43(5)
109.6(2)
113.2(2)
113.0(2)
107.9(2)
108.3(2)
104.5(2)
P(2)–Pt(1)–P(1)
P(2)–Pt(1)–S(1)
P(1)–Pt(1)–S(1)
S(1)–Pt(1)–Cl(1)
P(1)–Pt(1)–Cl(1)
P(2)–Pt(1)–Cl(1)
C(19)–Si(1)–C(13)
C(19)–Si(1)–C(2)
C(13)–Si(1)–C(2)
C(19)–Si(1)–C(7)
C(13)–Si(1)–C(7)
C(2)–Si(1)–C(7)
168.22(3)
94.46(4)
84.96(3)
172.66(4)
92.39(4)
86.74(4)
P(2)–Pt(1)–P(1)
P(1)–Pt(1)–S(2)
P(2)–Pt(1)–S(2)
P(1)–Pt(1)–S(1)
P(2)–Pt(1)–S(1)
S(2)–Pt(1)–S(1)
C(27)–Si(1)–C(26)
C(27)–Si(1)–C(33)
C(26)–Si(1)–C(33)
C(27)–Si(1)–C(21)
C(26)–Si(1)–C(21)
C(33)–Si(1)–C(21)
C(7)–Si(2)–C(2)
C(7)–Si(2)–C(14)
C(2)–Si(2)–C(14)
C(7)–Si(2)–C(8)
C(2)–Si(2)–C(8)
C(14)–Si(2)–C(8)
99.95(6)
84.04(6)
172.34(6)
163.35(6)
89.51(6)
88.24(6)
109.9(4)
109.0(4)
107.4(4)
110.4(3)
114.3(4)
105.7(3)
112.7(3)
112.5(4)
112.3(3)
106.0(4)
107.1(3)
105.7(3)
P(2)–Pt(1)–P(1)
P(1)–Pt(1)–S(2)
P(2)–Pt(1)–S(2)
P(1)–Pt(1)–S(1)
P(2)–Pt(1)–S(1)
S(2)–Pt(1)–S(1)
C(7)–Si(1)–C(14)
C(7)–Si(1)–C(2)
C(14)–Si(1)–C(2)
C(7)–Si(1)–C(8)
C(14)–Si(1)–C(8)
C(2)–Si(1)–C(8)
C(33)–Si(2)–C(26)
C(33)–Si(2)–C(21)
C(26)–Si(2)–C(21)
C(33)–Si(2)–C(27)
C(26)–Si(2)–C(27)
C(21)–Si(2)–C(27)
164.13(6)
83.26(6)
93.69(6)
96.63(6)
84.64(6)
173.46(6)
112.4(4)
114.2(7)
109.9(3)
106.0(3)
106.2(3)
107.7(3)
109.0(4)
110.1(3)
116.4(3)
108.1(3)
106.1(3)
106.7(3)
111.5(2)
114.33(19)
109.69(18)
106.83(18)
106.18(18)
107.90(16)
109.7(2)
a
Symmetry transformations used to generate equivalent atoms: b Àx + 1, y, z + 1.

V. Cordero-Pensado et al. / Inorganica Chimica Acta 359 (2006) 4007–4018
4011
microcrystalline orange powder. Yield: 72%. M.p. 210 ꢁC.
1H NMR (300 MHz, CDCl3), d 7.8–6.9 (m, Ph, 68H);
31P{1H} NMR (121 MHz, CDCl3), d 24.1 (s, JP–Pt
1.41 kHz, 2P-trans), 22.33 (s, JP–Pt = 1.38 kHz, 2P-cis).
Elem. Anal. Calc. for [C84H68P2PtS2Si2]: C, 69.35; H,
4.71. Found: C, 68.94; H, 4.64%. MS-FAB+ [M+] = 1454
m/z.
2.9. Data collection and refinement for trans-
[Pd(PPh3)2(SC6H4-2-SiPh3)2] (1),
z-[Pt(PPh3)2(Cl)(SC6H4-2-SiPh3)] (3),
e-[Pt(PPh3)2(Cl)(SC6H4-2-SiCH3Ph2)] (6),
cis-[Pt(PPh3)2(SC6H4-2-SiCH3Ph2)2] (7) and
trans-[Pt(PPh3)2(SC6H4-2-SiCH3Ph2)2] (8)
=
Crystalline red-orange prisms for 1, 3, 6, 7 and 8 were
grown by slow evaporation of CH2Cl2/MeOH solvent sys-
tems, and mounted on glass fibers. In all cases, the X-ray
intensity data were measured at 293 or 291 K on a Bruker
SMART APEX CCD-based X-ray diffractometer system
2.6. Synthesis of e-[Pt(PPh3)2(Cl)(SC6H4-2-SiCH3Ph2)]
(6)
To a CH2Cl2 solution (20 mL) of cis-[PtCl2(PPh3)2]
(49.7 mg, 0.063 mmol), a solution consisting of [C6H4SH-
2-CH3Ph2] (19 mg, 0.063 mmol) and NEt3 (0.1 mL,
0.063 mmol) in 10 mL of CH2Cl2 was added dropwise under
stirring. The resulting reaction mixture was allowed to stir
overnight. After this time, the reaction was filtered off and
the solvent evaporated under vacuum, to afford a microcrys-
talline yellow-orange powder. Yield: 84%. M.p. 115 ꢁC
˚
equipped with a Mo-target X-ray tube (k = 0.71073 A).
The detector was placed at a distance of 4.837 cm from
the crystals in all cases. A total of 1800 frames were col-
lected with a scan width of 0.3ꢁ in x and an exposure time
of 10 s/frame. The frames were integrated with the Bruker
SAINT software package [10] using a narrow-frame integra-
tion algorithm. The integration of the data was done using
a triclinic unit cell in all cases except for complex 1 where a
1
(decompose). H NMR (300 MHz, CDCl3), d 7.8–6.8 (m,
Ph, 44H), 1.35 (s, Me, 3H); 31P{1H} NMR (121 MHz,
CDCl3), d 21.3 (s, JP–Pt = 1.46 kHz, 1P-e configuration).
Elem. Anal. Calc. for [C55H47ClP2PtSSi]: C, 62.28; H, 4.47.
Found: C, 61.35; H, 4.40%. MS-FAB+ [M+] = 1060 m/z.
2.7. Synthesis of cis-[Pt(PPh3)2(SC6H4-2-SiCH3Ph2)2]
(7) and trans-[Pt(PPh3)2(SC6H4-2-SiCH3Ph2)2] (8)
To a CH2Cl2 solution (20 mL) of cis-[PtCl2(PPh3)2]
(49.7 mg, 0.063 mmol), a solution consisting of [C6H4SH-
2-CH3Ph2] (38.5 mg, 0.126 mmol) and NEt3 (0.23 mL,
0.146 mmol) in 10 mL of CH2Cl2 was added dropwise under
stirring. The resulting reaction mixture was allowed to stir
overnight. After this time, the reaction was filtered off and
the solvent evaporated under vacuum, to afford a microcrys-
talline orange powder. Yield: 76%. M.p. 125 ꢁC (decom-
pose). 1H NMR (300 MHz, CDCl3), d 7.8–6.8 (m, Ph,
58H), 1.35 (s, Me, 6H); 31P{1H} NMR (121 MHz, CDCl3),
d 23.6 (s, JP–Pt = 1.41 kHz, 2P-trans), 22.9 (s, JP–Pt
=
1.38 kHz, 2P-cis). Elem. Anal. Calc. for [C74H64P2PtS2Si2]:
C, 66.79; H, 4.85. Found: C, 65.25; H, 4.74%. MS-FAB+
[M+] = 1330 m/z.
2.8. Synthesis of [C6H4S-2-SiPh3]2 (9)
To a CH2Cl2 solution (10 mL) of trans-[NiCl2(PPh3)2]
(51.3 mg, 0.078 mmol), a solution consisting of [C6H4SH-
2-SiPh3] (57.4 mg, 0.156 mmol) and NEt3 (0.25 mL,
0.156 mmol) in 10 mL of CH2Cl2 was added dropwise
under stirring. The resulting reaction mixture was allowed
to stir overnight. After this time, the reaction was filtered
off and the solvent evaporated under vacuum, to afford a
microcrystalline brown-greenish powder. Yield: 68.7%.
M.p. 229 ꢁC. 1H NMR (300 MHz, CDCl3), d 7.76–7.12
(m, Ph). Elem. Anal. Calc. for [C48H38S2Si2]: C, 78.42; H,
5.21. Found: C, 77.64; H, 5.16%. MS-FAB+ [M+] = 734
m/z.
Fig. 1. An ORTEP representation of the structure of trans-
[Pd(PPh3)2(SC6H4-2-SiPh3)2] (1). Displacement ellipsoids are drawn at
50% probability level showing the atom labeling scheme. Hydrogen atoms
have been omitted for clarity.

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V. Cordero-Pensado et al. / Inorganica Chimica Acta 359 (2006) 4007–4018
Fig. 2. An ORTEP representation of the structure of z-[Pt(PPh3)2(Cl)(SC6H4-2-SiPh3)] (3). Displacement ellipsoids are drawn at 50% probability level
showing the atom labeling scheme. Hydrogen atoms have been omitted for clarity.
Fig. 3. An ORTEP representation of the structure of e-[Pt(PPh3)2(Cl)(SC6H4-2-SiCH3Ph2)] (6). Displacement ellipsoids are drawn at 50% probability level
showing the atom labeling scheme. Hydrogen atoms have been omitted for clarity.

V. Cordero-Pensado et al. / Inorganica Chimica Acta 359 (2006) 4007–4018
4013
monoclinic cell was used to yield a total of 14315, 60098,
3. Results and discussion
21456, 40097 and 36821 reflections for 1, 3, 6, 7 and 8,
˚
respectively, to a maximum 2h angle of 50.00ꢁ (0.93 A res-
The reaction in a 1:2 molar ratio of the starting material
trans-[PdCl2(PPh3)2] with [C6H4SH-2-SiPh3] or [C6H4SH-
2-SiCH3Ph2] in the presence of NEt3 as a base affords in
both cases the disubstituted product trans-[Pd(SR)2-
(PPh3)2] in good yields (Scheme 2).
olution), of which 6076 (1), 17749 (3), 9138 (6), 11829 (7)
and 11785 (8) were independent. Analysis of the data
showed in all cases negligible decays during data collec-
tions. The structures were solved by Patterson method
using SHELXS-97 [11] program. The remaining atoms were
located via a few cycles of least squares refinements and dif-
Analysis by 1H NMR reveals in both cases the presence
of the aromatic rings of the thiolate and PPh3 ligands. For
the particular case of complex trans-[Pd(PPh3)2(SC6H4-2-
SiMePh2)2] (3), in addition to these signals, a peak at
2.7 ppm due to the presence of the CH3 substituent in
the thiol is also observed. The trans configuration for the
two complexes can be concluded from the analysis of their
31P{1H} NMR spectra, where for trans-[Pd(PPh3)2(SC6H4-
2-SiPh3)2] (1) and trans-[Pd(PPh3)2(SC6H4-2-SiMePh2)2]
(2), narrow single signals are observed at 24.65 and
29.31 ppm, respectively, which is clearly indicative of both
phosphorus nuclei to be present in equal magnetic environ-
ments. Analysis by MS-FAB+ of the two compounds
reveals similar fragmentation patterns. For the two com-
plexes, the presence of molecular ions was the result of a
primary fragmentation of one thiolate and one PPh3 to
afford peaks at [MÀ(PPh3-SR)+] = 735 m/z and 673 m/z
ꢀ
ference Fourier maps, using the space group P1 in all cases
except for complex 1 where a C2 space group was
employed and with Z = 2 for all compounds except com-
plex 3 which presented a Z = 4. Hydrogen atoms were
input at calculated positions, and allowed to ride on the
atoms to which they are attached. Thermal parameters
were refined for hydrogen atoms on the phenyl groups with
Uiso(H) = 1.2Ueq of the parent atom in all cases. For all
complexes, the final cycle of refinement was carried out
on all non-zero data using SHELXL-97 [11] and anisotropic
thermal parameters for all non-hydrogen atoms. The
details of the structure determinations are given in Table
˚
1 and selected bond lengths (A) and angles (ꢁ) are given
in Table 2, respectively. The numbering of the atoms is
shown in Figs. 1–4, respectively (ORTEP) [12].
Fig. 4. An ORTEP representation of the structure of cis-[Pt(PPh3)2(SC6H4-2-SiCH3Ph2)2] (7). Displacement ellipsoids are drawn at 50% probability level
showing the atom labeling scheme. Hydrogen atoms have been omitted for clarity.

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V. Cordero-Pensado et al. / Inorganica Chimica Acta 359 (2006) 4007–4018
for trans-[Pd(PPh3)2(SC6H4-2-SiPh3)2] (1) and trans-
[Pd(PPh3)2(SC6H4-2-SiMePh2)2] (2), respectively. Elemen-
tal analysis in both cases agreed well with the proposed
formulations. The trans configuration for these complexes
was unequivocally demonstrated by single crystal X-ray
diffraction experiments of complex trans-[Pd(PPh3)2-
(SC6H4-2-SiPh3)2] (1). Crystals of 1 suitable for this analy-
sis were grown from a double layer solvent system CH2Cl2/
MeOH. The crystal structure shows the palladium center
to be in a slightly distorted square planar geometry, having
the two (SC6H4-2-SiPh3) moieties in a trans arrangement
and completing the coordination of the two PPh3 ligands
(Fig. 1). It is noteworthy that the molecule of complex 1
has an exact crystallographic inversion symmetry, with
the Pd atom lying on an inversion center. The bond dis-
tances and bond angles are found to be within the expected
values (Table 2).
Analogous reactions with cis-[PtCl2(PPh3)2] and the thi-
ols [C6H4SH-2-SiPh3]/[C6H4SH-2-SiCH3Ph2] in the pres-
ence of NEt3 as a base exhibited a different behavior than
that shown for trans-[PdCl2(PPh3)2]. In the case of the reac-
1
tion with [C6H4SH-2-SiPh3], analysis by H NMR of the
crude product revealed a multiplet between 6.6 and
7.4 ppm due to the presence of the protons in the aromatic
rings of the PPh3 and the thiolate ligands. Determination
of the 31P{1H}NMR spectrum exhibits the presence of dif-
ferent peaks, where two main independent signals can be
identified: one at 22.33 ppm with a JP–Pt = 1.38 kHz due
to the presence of the disubstituted product
[Pt(PPh3)2(SC6H4-2-SiPh3)2] (4) in a cis configuration and
Ph
Ph3P
Cl
Cl
Si
NEt3
R
Si
Pd
2
R
+
Ph3P
S
S
Ph
PPh3
SH
Pd
Ph
R
PPh3
Si
Ph
R= Me, Ph
Scheme 2. General synthesis of complexes of the type trans-[Pd(PPh3)2(SC6H4-2-Si(R)Ph2)2].
Ph
Ph3P
Ph3P
Cl
Cl
Si
NEt3
R
Si
Pt
2
R
+
Ph3P
S
S
Ph
SH
Pt
Ph
R
PPh3
Si
Ph
R= Me, Ph
Ph
R
Si
Ph3P
S
S
Ph
Ph
Pt
Ph3P
Si
R
Ph
Ph3P
S
Cl
PPh3
Pt
Ph
Ph3P
Cl
Cl
Si
NEt3
Pt
R
+
Si
R
Ph
Ph3P
SH
R= Me, Ph
Scheme 3. General synthesis of the platinum complexes cis/trans-[Pt(PPh3)2(SC6H4-2-Si(R)Ph2)2] and e/z À [Pt(PPh3)2(Cl)(SC6H4-2-Si(R)Ph2)].

V. Cordero-Pensado et al. / Inorganica Chimica Acta 359 (2006) 4007–4018
4015
the other at 24.07 ppm with a JP–Pt = 1.41 kHz due to the
presence of the disubstituted complex [Pt(PPh3)2(SC6H4-
2-SiPh3)2] (5) in a trans configuration. It is also possible
to observe a small peak at 20.74 ppm with a JP–Pt
=
1.47 kHz, which can be attributed to the single substituted
complex [Pt(PPh3)2(Cl)(SC6H4-2-SiPh3)] (3) in an z config-
uration. In fact, further examination of this reaction by
31P{1H} NMR spectra in their early stages shows that after
5 min reaction time, the only clearly distinguishable prod-
uct is the monosubstituted product z-[Pt(PPh3)2(Cl)-
(SC6H4-2-SiPh3)] (3), with a unique singlet at 20.74 ppm
and its corresponding platinum satellites for a coupling
constant of JP–Pt = 1.47 kHz. At this time, the signals cor-
responding to the formation of the other two identifiable
species start to emerge from the baseline of the spectrum.
Attempts to separate the cis and trans isomers by column
chromatography resulted in the decomposition of the prod-
ucts. Thus, in an attempt to separate the products we
decided to try the recrystallization of the complexes from
the crude mixture. Hence, recrystallization from a double
layer system CH2Cl2/MeOH afforded a small amount of
yellow crystals of z-[Pt(PPh3)2(Cl)(SC6H4-2-SiPh3)] (3).
This compound was actually synthesized in a pure manner
by carrying out the reaction in a 1:1 molar ratio thiol:plat-
inum, showing that the number of thiolates included in the
coordination of the platinum center can be controlled
(Scheme 3). Several other attempts to separate complexes
4 and 5 were unsuccessful. We believe that complexes 4
and 5 inter-convert in solution, thus making their separa-
tion difficult.
The aforementioned crystals of z-[Pt(PPh3)2(Cl)(SC6H4-
2-SiPh3)] (3) were analyzed by single crystal X-ray diffrac-
tion analysis showing unequivocally the identity of com-
plex 3, having the platinum center in a slightly distorted
square planar environment with both PPh3 ligands accom-
modated in a cis configuration and completing the coordi-
nation one thiolate and one chloride ligand (Fig. 2). The
bond distances and angles in this complex are normal
and within the expected values (Table 2).
A similar behavior is observed when the reaction
between cis-[PtCl2(PPh3)2] and the thiol [C6H4SH-2-
SiCH3Ph2] was carried out, the result being evident from
the 31P{1H} and the presence of two main species corre-
sponding to the disubstituted product in both the cis and
trans configurations cis-[Pt(PPh3)2(SC6H4-2-SiCH3Ph2)2]
Fig. 5. An ORTEP representation of the structure of trans-
[Pt(PPh3)2(SC6H4-2-SiCH3Ph2)2] (8). Displacement ellipsoids are drawn
at 50% probability level showing the atom labeling scheme. Hydrogen
atoms have been omitted for clarity.
to a slightly distorted square planar environments. Addi-
tionally, the two structures show the presence of solvent
crystallization molecules for (7) one CH2Cl2 molecule and
two of the same solvent for complex 8, which are presented
disordered in the lattice.
Furthermore,
complex
e-[Pt(PPh3)2(Cl)(SC6H4-2-
SiCH3Ph2)] (6) was selectively obtained from the equimolar
reaction of cis-[PtCl2(PPh3)2] and the thiol [C6H4SH-2-
SiCH3Ph2] in the presence of NEt3 as a base. From this
reaction, crystals suitable for single crystal X-ray diffrac-
tion analysis were obtained. The results obtained showed
the presence of a platinum center in a slightly distorted
square planar geometry, with the two PPh3 ligands in a
(7),
23.57 ppm with a JP–Pt = 1.41 kHz and 22.91 ppm with a
JP–Pt = 1.38 kHz, respectively, and small peak at
trans-[Pt(PPh3)2(SC6H4-2-SiCH3Ph2)2]
(8)
at
a
21.3 ppm with a JP–Pt = 1.46 kHz due to the presence of
the monosubstituted e configured product [Pt(PPh3)2(Cl)-
(SC6H4-2-SiCH3Ph2)] (6).
Recrystallization of the crude product from a CH2Cl2/
MeOH solvent system afforded two different sorts of crys-
tals suitable for X-ray diffraction analysis that confirm
unequivocally both the cis (Fig. 4) and trans (Fig. 5) config-
urations for complex [Pt(PPh3)2(SC6H4-2-SiCH3Ph2)2]. In
both cases, the structures exhibit the platinum center in
S
S
Ph3Si
SiPh3
Scheme 4. Structure of the disulfide (SC6H4-2-SiPh3)2.

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V. Cordero-Pensado et al. / Inorganica Chimica Acta 359 (2006) 4007–4018
trans configuration and completing the coordination one
thiolate and one chloride ligand. Besides, the structure
shows the presence of one crystallization molecule of
CH2Cl2, this molecule is found disordered in the lattice
(Fig. 3).
increased by steric effects that in the particular case of com-
plexes 7 and 8 may be more notorious due to the inherent
steric effect of both thiolates in the complex, which in turn
will be more pronounced in the case of complex 7 due to
the cis configuration of the thiolates.
For these structures, the Pd–S distances are slightly dif-
Noteworthy is the fact that the number of structurally
analyzed compounds with the kernel cis-[Pt(SR)2(PPh3)2]
is comparably large with respect to the corresponding trans
isomers. This must be attributed to the fact that merely bi-
dentate ligands such as S–S ligands [13,14], P–P ligands
[15], or both types [13,16] were used allowing exclusively
cis arrangement and at the same time avoiding the very well
known polymerization of these complexes. Thus, examples
of motifs with exclusively mono-dentate S and P ligands in
˚
ferent being of Pt(1)–S(1) 2.3061(9) A for 6, Pt(1)–S(1)
˚
2.3476(17) and Pt(1)–S(2) 2.3723(17) A for 7 and Pt(1)–
˚
S(1) 2.3402(16) and Pt(1)–S(1) 2.3275(16) A for 8. The vari-
ations in these bond distances might be a consequence of
several factors, including the difference in trans effect of
the different substituents in the three complexes being one
chloride in the case of 6, one thiolate in the case of 7 and
a triphenylphosphine in the case of 8. This effect can be
R
R= Me, Ph
Si
Si
S
S
R
Cl
Ph3P
PPh3
Cl
Ni
NEt3
Si
R
SH
Cl
PPh3
Cl
Ph3P
Ph3P
Cl
Cl
Pd
Pt
Ph3P
NEt3
NEt3
R= Me, Ph
Ph
Ph
R
Si
R
Si
Ph3P
S
S
Ph
S
PPh3
S
Ph
Pt
Pd
Ph
R
Ph
PPh3
Ph
R
Ph
Ph3P
Si
Si
Ph
R
Si
Ph3P
Ph3P
S
S
Ph
Ph
Pt
Si
R
Ph
Scheme 5.

V. Cordero-Pensado et al. / Inorganica Chimica Acta 359 (2006) 4007–4018
4017
a cis arrangement are rare [17] and those bearing a trans
configuration are even rarer.
search by CONACYT (J41206-Q) and PAPIIT (IN114605)
is gratefully acknowledged.
Reactions with the analogous nickel derivative trans-
[NiCl2(PPh3)2] and the thiols [C6H4SH-2-SiPh3] or
[C6H4SH-2-SiCH3Ph2] were also attempted, affording in
both cases microcrystalline brown powders and the precip-
itation of some gray material presumably Ni(0) as a conse-
quence of the decomposition of the starting material
trans-[NiCl2(PPh3)2]. The brown powder obtained from
the reaction with the thiol [C6H4SH-2-SiPh3] was analyzed
by proton NMR showing signals between 7.1 and 7.6 ppm
due to the presence of aromatic protons. Further analysis
of this compound by MS-FAB+ afforded valuable informa-
tion by showing a peak at 734 m/z, which could be assigned
to the disulfide (SC6H4-2-SiPh3)2 product of the oxidation
of thiol by the nickel complex. Recrystallization of this
product afforded crystals suitable for X-ray diffraction
analysis, which indeed showed the identity of the com-
pound to be the already known disulfide (SC6H4-2-SiPh3)2
[18] (see Scheme 4).
To sum up, we have synthesized and characterized some
derivatives of the sterically hindered thiols [C6H4SH-2-
SiPh3] or [C6H4SH-2-SiCH3Ph2] with transition metals of
group 10. In the case of palladium, the reactions are selec-
tive to the formation of the disubstituted complexes trans-
[Pd(PPh3)2(SC6H4-2-SiRPh2)2] (R = Me, Ph). While in the
case of platinum the reaction affords a mixture of the mono
and disubstituted species [Pt(PPh3)2(Cl)(SC6H4-2-SiRPh2)]
(R = Me, Ph) and cis/trans-[Pd(PPh3)2(SC6H4-2-SiRPh2)2]
(R = Me, Ph); this probably being due to the size of plati-
num which allows the accommodation of the ligands in a
more comfortable way both in the cis and trans configura-
tions. Stoichiometric control of this reaction gives place in
a clean manner to the formation of the monosubstituted
species [Pt(PPh3)2(Cl)(SC6H4-2-SiRPh2)] (R = Me, Ph);
recently these species have become very important in orga-
nometallic chemistry due to the fact that they are consid-
ered as useful systems for the mechanistic studies of C–S
cross-coupling reactions. Thus, efficient synthesis of this
sort of complexes is currently highly valued [19] (see
Scheme 5).
Appendix A. Supplementary material
Supplementary data for complexes 1, 3, 6, 7 and 8 have
been deposited at the Cambridge Crystallographic Data
Centre. Copies of this information are available free of
charge on request from The Director, CCDC, 12 Union
Road, Cambridge CB2 1EZ, UK (fax: +44 1223 336 033;
e-mail: deposit@ccdc.cam.ac.uk or www: http://
www.ccdc.cam.ac.uk) quoting the deposition numbers
CCDC 296859–296863. Supplementary data associated
with this article can be found, in the online version, at
doi:10.1016/j.ica.2006.05.018.
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