Transmetallation reactions of [Sn(R)2(Ph2 PC6H4-2-S)2] with metal complexes of the Group 10 Stereoselective synthesis of cis-[M(Ph2PC6H4-2-S)2] (M=Ni, Pd, Pt)

Article abstract of DOI:10.1016/S0022-328X(03)00538-2

The complexes cis-[M(Ph₂PC₆H₄-2-S) ₂] M=Ni, Pd, Pt were stereoselectively synthesized by transmetallation reactions of [M(Cl)₂(NCC₆ H₅)₂] M=Pd, Pt or NiCl₂·6H₂O with [Sn(R)₂(Ph₂PC₆H₄-2-S) ₂] R=Ph, ⁿBu or ^tBu. The conformation of the Pd and Pt derivatives being unequivocally confirmed by single crystal X-ray diffraction studies showing both metal centers to be into a slightly distorted square planar environment, the main distortion being due to the steric hindrance caused by the aromatic rings in the phosphine moiety.

Full text of DOI:10.1016/S0022-328X(03)00538-2

Journal of Organometallic Chemistry 679 (2003) 101Á109
/
www.elsevier.com/locate/jorganchem
Transmetallation reactions of [Sn(R)2(Ph2PC6H4-2-S)2] with metal
complexes of the Group 10
Stereoselective synthesis of cis-[M(Ph2PC6H4-2-S)2] (Mꢀ
/
Ni, Pd, Pt)
Daniel Canseco-Gonza´lez, Valente Go´mez-Ben´ıtez, Simo´n Herna´ndez-Ortega,
Rube´n A. Toscano, David Morales-Morales *
Instituto de Qu´ımica, Universidad Nacional Auto´noma de Me´xico, Cd. Universitaria, Circuito Exterior, Coyoaca´n, 04510 Me´xico city, D.F., Me´xico
Received 6 May 2003; received in revised form 3 June 2003; accepted 6 June 2003
Abstract
The complexes cis-[M(Ph2PC6H4-2-S)2] Mꢀ
/
Ni, Pd, Pt were stereoselectively synthesized by transmetallation reactions of
Ph, nBu or t Bu. The conformation of the Pd and
[M(Cl)2(NCC6H5)2] MꢀPd, Pt or NiCl2×6H2O with [Sn(R)2(Ph2PC6H4-2-S)2] Rꢀ
/
/
/
Pt derivatives being unequivocally confirmed by single crystal X-ray diffraction studies showing both metal centers to be into a
slightly distorted square planar environment, the main distortion being due to the steric hindrance caused by the aromatic rings in
the phosphine moiety.
# 2003 Elsevier B.V. All rights reserved.
Keywords: Phosphorus-sulfur ligands; Transmetallation; Transition metal complexes; Crystal structures
1. Introduction
ing. Moreover, the presence of these ligands in the
coordination sphere of transition metal complexes may
render interesting behaviours in solution as these ligands
can be capable of full or partial de-ligation (hemilability)
[6], being able to provide important extra coordination
sites for incoming substrates during a catalytic process
[6]. In this respect, processes involving transmetallation
reactions as key steps for a particular catalytic process
have been of considerable interest in the recent years
and this is particularly true for reactions involving the
In recent years, attention has increasingly been paid
to the coordination chemistry of polydentate ligands
incorporating both thiolate and tertiary phosphine
donor ligands, as their combination is likely to confer
unusual structures and reactivities on their metal com-
plexes [1]. Some of these complexes have been used as
models of biologically active centers in metalloproteins
such as ferredoxins, nitrogenase, blue copper proteins
and metallothioneins [2] or as models for the design of
complexes with potential application as radiopharma-
ceuticals [3]. These complexes have shown an intriguing
variety of structures [4] or unusual oxidation states and
enhanced solubility [5], making these species excellent
candidates for further studies in reactivity. In the
specific case of compounds with elements of the groups
formation of CÃ/C bonds and of particular interest the
Stille reaction [7] which uses organometallic tin com-
plexes as starting materials and where the transmetalla-
tion process is the rate-determining step. Thus,
following our current interest [8] in the design and
synthesis of new complexes containing the Ph2PC6H4-2-
SH1 (phPSH) hybrid proligand we would like to report
our findings on the reactivity of the organometallic
tin(IV) compounds [Sn(R)2(Ph2PC6H4-2-S)2] with
Ni(II), Pd(II) and Pt(II) complexes.
8Á10 these may be suitable species for catalytic screen-
/
* Corresponding author. Tel.: ꢁ
/
52-555-622-4514; fax: ꢁ52-555-
/
616-2217.
1
E-mail address: damor@servidor.unam.mx (D. Morales-Morales).
Diphenyl(phenyl-2-thiol)phosphine.
0022-328X/03/$ - see front matter # 2003 Elsevier B.V. All rights reserved.
doi:10.1016/S0022-328X(03)00538-2

102
D. Canseco-Gonza´lez et al. / Journal of Organometallic Chemistry 679 (2003) 101Á109
/
2. Experimental
2.2.1. [Sn(Ph)2(Ph2PC6H4-2-S)2] (1)
Ph2PC6H4-2-SH (200 mg, 0.68 mmol), NEt3 (71 mg,
0.70 mmol) and [Sn(Ph)2Cl2] (117 mg, 0.34 mmol).
1
2.1. Materials and methods
Yield: 80.67%. H-NMR (300 MHz, CDCl3), d 7.65Á
/
6.50 (m, Ph, 38H); 31P-NMR (121 MHz, CDCl3), d ꢂ
13.10 (s). Anal. Calc. for [C48H38P2S2Sn]: C, 67.8; H,
4.4. Found: C, 68.5; H, 4.2%. MS-FABꢁ [Mꢁ]ꢀ
859
/
Unless stated otherwise, all reactions were carried out
under an atmosphere of dinitrogen using conventional
Schlenk glassware, solvents were dried using established
procedures and distilled under dinitrogen immediately
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
parts per million down field of TMS using the solvent
/
m/z.
2.2.2. [Sn(nBu)2(Ph2PC6H4-2-S)2] (2)
Yield: 61.32%. 1H-NMR (300 MHz, CDCl3), d 7.63Á
/
n
7.00 (m, Ph, 28H), 1.72Á
(121 MHz, CDCl3), d ꢂ
[C44H46P2S2Sn]: C, 64.50; H, 5.60. Found: C, 63.70;
H, 5.40%. Ms-FABꢁ [Mꢁ]ꢀ
819 m/z.
/
0.72 (m, Bu, 18H); 31P-NMR
/
11.70 (s). Anal. Calc. for
(CDCl3, dꢀ
7.27) as internal standard. 31P-NMR (121
/
/
MHz) spectra were recorded with complete proton
decoupling and are reported in parts per million using
85% H3PO4 as external standard. Elemental analyses
2.2.3. [Sn(tBu)2(Ph2PC6H4-2-S)2] (3)
Ph2PC6H4-2-SH (200 mg, 0.68 mmol), NEt3 (71 mg,
0.70 mmol) and [Sn(tBu)2Cl2] (103 mg, 0.34 mmol).
were determined on a PerkinÁ
/
Elmer 240. Positive-ion
FAB mass spectra were recorded on a JEOL JMS-
SX102A mass spectrometer operated at an accelerating
voltage of 10 kV. Samples were desorbed from a
nitrobenzyl alcohol matrix using 3 keV xenon atoms.
Mass measurements in FAB are performed at a resolu-
tion 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. The proligand (Ph2PC6H4-2-SH) phPSH [9] was
1
Yield: 95.51%. H-NMR (300 MHz, CDCl3), d 7.77Á
/
6.70 (m, Ph, 28H), 1.22 (s, tBu, 12H), 1.33 (s, tBu, 6H);
31P-NMR (121 MHz, CDCl3), d ꢂ
11.80 (s). Anal. Calc.
for [C44H46P2S2Sn]: C, 64.50; H, 5.60. Found: C, 62.90;
H, 6.00%. MS-FABꢁ [Mꢁ]ꢀ
819 m/z.
/
/
2.3. Synthesis of cis-[Pd(Ph2PC6H4-2-S)2] (4)
To a solution of [Sn(R)2(Ph2PC6H4-2-S)2] (Rꢀ
/
Ph, 50
Bu,
synthesized according to the published procedure and
n
Ph, Bu or
mg, 0.058 mmol, RꢀnBu, 48 mg, 0.058 mmol, Rꢀt
/
/
the complexes [Sn(R)2(Ph2PC6H4-2-S)2] Rꢀ
/
48 mg, 0.058 mmol) in CH2Cl2 (20 ml), a CH2Cl2
solution (30 ml) of [Pd(Cl)2(NCC6H5)2] (22 mg, 0.058
mmol) was added under stirring. The resulting mixture
was allowed to stir overnight. After this time, formation
of a pale yellow precipitated was noticed, the product
was filtered off under vacuum and washed twice with
methanol. Recrystallization from a double layer solvent
system CH2Cl2/MeOH afforded complex 4 as a micro-
tBu where prepared by a slight modification of the
method reported [10]. The starting materials
[M(Cl)2(NCC6H5)2] MꢀPd [11], Pt [12] were prepared
/
according to published procedures.
2.2. Synthesis of the metalloligands
n
Ph, (1) Bu (2) and
[Sn(R)2(Ph2PC6H4-2-S)2] Rꢀ
/
1
crystalline yellow powder. Yield: 87.5%. H-NMR (300
MHz, CDCl3), d 7.71Á
6.79 (m, Ph, 28H); 31P-NMR
(121 MHz, CDCl3), d, 42.42 (s). Anal. Calc. for
tBu (3)
/
All complexes were synthesized by a slight modifica-
tion of the methods reported [10]. Thus as a representa-
tive example the experimental procedure for the
synthesis of complex 2 is described.
[C36H28P2S2Pd]: C, 64.20; H, 4.00. Found: C: 64.00,
H: 4.20%. MS-FABꢁ [Mꢁ]ꢀ
692 m/z.
/
A solution of the proligand Ph2PC6H4-2-SH (200 mg,
0.68 mmol) and NEt3 (71 mg, 0.70 mmol) in dry-
methanol (35 ml) was refluxed for 5 min. After this time
the heating is stopped and a methanol solution (15 ml)
of [Sn(nBu)2Cl2] (103 mg, 0.34 mmol) was then added.
The resulting mixture is refluxed for further 4 h (a
gradual cloudiness is observed with time). After this
time the solution was cooled to room temperature and
the resulting white precipitate is washed twice with
methanol (25 ml) and filtered off under vacuum. Yield
61% of a white microcrystalline powder of 2.
2.4. Synthesis of cis-[Pt(Ph2PC6H4-2-S)2] (5)
The compound was synthesized and purified in a
similar manner to that of complex
4
from
[Sn(Ph)2(Ph2PC6H4-2-S)2] (50 mg, 0.058 mmol) and
[Pt(Cl)2(NCC6H5)2] (22.3 mg, 0.058 mmol) as the source
of platinum. Yield: 80.61%. 1H-NMR (300 MHz,
CDCl3), d 7.73Á
6.74 (m, Ph, 28H); 31P-NMR (121
/
MHz, CDCl3), d, 42.94 (s, JPÃPt 2680 Hz). Anal. Calc.
for [C36H28P2S2Pt]: C, 55.30; H, 3.60. Found: C, 55.90;
H, 3.30%. MS-FABꢁ [Mꢁ]ꢀ
781 m/z.
/

D. Canseco-Gonza´lez et al. / Journal of Organometallic Chemistry 679 (2003) 101Á
/109
103
2.5. Synthesis of cis-[Ni(Ph2PC6H4-2-S)2] (6)
3. Results and discussion
3.1. Synthesis and characterization of the metalloligands
The title compound was synthesized and purified in a
n
Ph(1), Bu(2) or
[Sn(R)2(Ph2PC6H4-2-S)2] Rꢀ
/
similar manner to that of complex
[Sn(Ph)2(Ph2PC6H4-2-S)2] (50 mg, 0.058 mmol) and
4
from
tBu(3)
1
6H2O (14 mg, 0.058 mmol). Yield: 87.5%. H-
NiCl2×
/
The three tin(IV) complexes were synthesized by a
slight modification of the reported technique [10]. In all
cases the complexes where obtained as colorless micro-
crystalline powders in good yields. Comparative analysis
by multinuclear NMR, FABꢁ-MS and elemental ana-
lysis agree well with the proposed formulations, the new
complex 2 containing n-butyl moieties was also analyzed
in a similar manner to that of the phenyl and tert-butyl
analogues. Crystals of 2 suitable for single crystal X-ray
diffraction analysis where obtained by slow evaporation
of a saturated solution of 2 in ethanol. The crystal
structure (Fig. 1) exhibits the tin center to be in a quasi-
NMR (300 MHz, CDCl3), d 7.76Á6.88 (m, Ph, 28H);
/
31P-NMR (121 MHz, CDCl3), d, 42.69 (s). Anal. Calc.
for [C36H28P2S2Ni]: C, 67.0; H, 4.3. Found: C, 65.7; H,
4.4%. MS-FABꢁ [Mꢁ]ꢀ
644 m/z.
/
2.6. Data collection and refinement for
[Sn(nBu)2(Ph2PC6H4-2-S)2] (2), cis-[Pd(Ph2PC6H4-
2-S)2] (4) and cis-[Pt(Ph2PC6H4-2-S)2] (5)
A crystalline colorless prism of 2, an orange prism of
4 and a yellow prism of 5 grown independently from
CH2Cl2/MeOH solvent systems were glued to glass
fibers. The X-ray intensity data were measured at 293
K for 2 and at 291 K for 4 and 5 on a Bruker SMART
APEX CCD-based X-ray diffractometer system
perfect tetrahedral environment with C(1)Ã
/
Sn(1)Ã
/
S(1)#1 and C(1)#1Ã
/
Sn(1)Ã
/
C(1)#1 angles equal to
106.7(3)8 and 105.3(3)8, respectively, the phPSꢂ ligands
are coordinated to the tin center as pendant arms with
only the sulfur atom attached to the metal, leaving the
phosphorus atoms free for further coordination (Fig. 1),
this coordination fashion was also confirmed by 31P-
NMR experiments where the difference in chemical
equipped with a Mo-target X-ray tube (lꢀ0.71073
/
˚
A). The detector was placed at a distance of 4.837 cm.
from the crystals in all cases. A total of 1800 frames were
collected with a scan width of 0.38 in v and an exposure
time of 10 s frameꢂ1. The frames were integrated with
the Bruker SAINT software package using a narrow-
frame integration algorithm. The integration of the data
was done using a orthorhombic unit cell for 2 or a
monoclinic unit cell for 4 and 5 to yield a total of 3658,
26 645 and 6115 reflections, respectively to a maximum
shifts observed for the free ligand (dꢀ
that of the coordinated ligand (dꢀ
not vary considerably (Ddꢀ0.6 ppm) thus indicating
/
ꢂ
/
12.3 ppm) and
/
ꢂ
/
11.7 ppm) does
/
the electronic environment around the phosphorus
atoms has remain unaltered. All other bond distances
and bond angles are within the expected values and
comparable to those observed in the phenyl derivative
[Sn(Ph)2(Ph2PC6H4-2-S)2] [16].
˚
2u angle of 50.008 (0.93 A resolution), of which 3658 (2),
5879 (4) and 5882 (5) were independent. Analysis of the
data showed in all cases negligible decays during data
collection. The structures were solved by Patterson
method using SHELXS-97 [13] program. The remaining
atoms were located via few cycles of least squares
refinements and difference Fourier maps, using the
3.2. Transmetallation reactions of [Sn(R)2(Ph2PC6H4-
2-S)2] with metal complexes of the Group 10
The synthesis of the organometallic complexes
t
Ph, Bu and its reactivity
[Sn(R)2(Ph2PC6H4-2-S)2] Rꢀ
/
with metals of the Group 11 (Ag, Au) have been
previously described [10], from all the probable fashions
in which these complexes may coordinate (Scheme 1),
binding to the corresponding metal by the free phos-
phorus atoms has been the common denominator. For
instance in the particular case of silver and gold, each
phosphorus coordinates independently to a metal center
(d in Scheme 1).
space groups Pcan with Zꢀ
/
4 (2), P21/n with Zꢀ4
/
(4) and P21/n with Zꢀ4 (5), respectively. 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 using a Ueqꢀ1.2 A to precedent atom.
/
The final cycle of refinement was carried out on all non-
zero data using SHELXL-97 [14] and anisotropic thermal
parameters for all non-hydrogen atoms. The details of
the structure determinations are given in Table 1. The
Thus, we decide to explore the reactivity of these
potential bidentate metalloligands with starting materi-
als of the Group 10 (Ni, Pd and Pt). In this way, by
reacting the complexes [Sn(R)2(Ph2PC6H4-2-S)2] Rꢀ
/
numbering of the atoms (ORTEP) [15] and selected bond
˚
lengths (A) and angles (8) are shown in Figs. 1Á3,
Ph, nBu or tBu with the starting material
[Pd(Cl)2(NCC6H5)2] in a 1:1 ratio, the complex cis-
[Pd(Ph2PC6H4-2-S)2] (4) was obtained irrespectively of
the R group, this compound being produced by a
/
respectively.

104
D. Canseco-Gonza´lez et al. / Journal of Organometallic Chemistry 679 (2003) 101Á109
/
Table 1
Summary of crystal structure data for complexes [Sn(n Bu)2(Ph2PC6H4-2-S)2] (2), cis-[M(Ph2PC6H4-2-S)2] Mꢀ
Pd (4), Pt (5)
/
Empirical formula
Formula weight
Temperature (K)
C44H46P2S2Sn (2)
819.56
293(2)
C36H28P2S2Pd (4)
777.97
291(2)
C36H28P2S2Pt (5)
866.66
291(2)
˚
Wavelength (A)
0.71073
Orthorhombic
Pcan
0.71073
Monoclinic
P21/n
0.71073
Monoclinic
P21/n
Crystal system
Space group
Unit cell dimensions
˚
a (A)
10.801(1)
14.854(1)
25.833(2)
90
15.5474(7)
9.5188(4)
22.5548(10)
90
15.5522(16)
9.538(7)
22.537(12)
90
˚
b (A)
˚
c (A)
a (8)
b (8)
l (8)
90
90
91.9180(10)
90
91.947(10)
90
3
˚
V (A )
4144.3(7)
4
3336.1(3)
4
1.549
3341.3(5)
4
1.723
Z
Dcalc (g cmꢂ3
Absorption coefficient (mmꢂ1
F(0 0 0)
)
1.314
0.823
1688
)
0.965
1576
4.607
1704
Crystal size (mm)
0.36ꢃ
25.00
h 512, 05
/
0.36ꢃ
/
0.10
0.28ꢃ
1.57Á25.00
185h 5
26
/
0.12ꢃ
/
0.10
0.22ꢃ
1.57Á24.99
05h 518, 05
26
6115
5882 [Rint
Integration
/
0.18ꢃ
/
0.16
u Range for data collection (8) 2.09Á
Index ranges
/
/
/
05
30
3658
/
/
/k 5
/
17, 05
/
l 5
/
ꢂ/
/
/18, ꢂ115
/
/
k 5
/
11, ꢂ
/
265
/
l 5
/
/
/
/k 5
/
11, ꢂ
/
265
/
l 5
/
Reflections collected
Independent reflections
Absorption correction
Refinement method
26 645
5879 [Rint
None
3658 [Rint
None
ꢀ/
0.0000]
ꢀ
/0.0539]
ꢀ/0.0500]
Full-matrix least-squares on F2 Full-matrix least-squares on F2
Full-matrix least-squares on F2
Data/restraints/parameters
Goodness-of-fit on F2
3658/0/223
1.020 a
5879/0/397
0.942 a
5882/0/398
0.896 a
Final R indices [I ꢀ
/
2s(I)]
R1ꢀ
R1ꢀ
0.553 and ꢂ
/0.0703, wR2ꢀ
/
0.1410 a
0.1887 b
R1ꢀ
/
0.0383, wR2ꢀ
/
0.0786 a
R1ꢀ
R1ꢀ
1.032 and ꢂ
/0.0397, wR2ꢀ
/
0.0769 a
0.0827 b
R indices (all data)
Largest difference peak and
hole
/0.1658, wR2ꢀ
/
R1
ꢀ/0.0549, wR2ꢀ
/
0.0830 b
˚
0.706 e A
/0.0692, wR2ꢀ
/
ꢂ3
ꢂ3
ꢂ3
˚
˚
/
0.487 e A
0.836 and ꢂ
/
/
1.087 e A
a
Sꢀ
/
[w(Fo)2ꢂ
/
(Fc)2)2/(nꢂ
/
p)]1/2 where nꢀ
/
number of reflections and pꢀtotal number of parameters.
/
b
R1ꢀ Fcj/jFoj, wR2ꢀ
/
jFoꢂ
/
/
[w((Fo)2ꢂ(Fc)2)2/w(Fo)2]1/2
/
.
transmetallation process. Analysis by FABꢁ-MS of this
complex exhibits a signal corresponding to the molecu-
suitable for X-ray diffraction analysis were obtained
from a CH2Cl2/MeOH double layer system as yellow
orange prisms and show the compound [Pd(Ph2PC6H4-
2-S)2] (4) to be in a cis conformation. The crystal
structure (Fig. 2) of this complex shows the Pd center in
lar ion at m/zꢀ
distribution [17]. An additional peak corresponding to
the loss of the fragment phPS is observed at m/zꢀ399.
/692 with the appropriate isotope
/
1
The H-NMR spectrum of this complex only exhibits
the signals due to the presence of the aromatic rings in
the molecule. The 31P-NMR is more informative as one
peak is observed at 42.42 ppm this signal being due to
the presence of the cis isomer. The same sample was left
to stand for 24 h. to allow the process to reach
equilibrium, after this time the 31P-NMR experiment
was carried out and two peaks were observed, one at
42.42 ppm and the other at 53.62 ppm in a 1.5:1 ratio,
the first and more intense signal being due to the
presence of the cis isomer and the other peak at higher
field due to the known trans isomer2 [18]. Crystals of 4
a distorted square planar environment (P(1)Ã
/
Pd(1)Ã
/
S(2), 171.66(4)8; P(2)Ã
/
Pd(1)Ã
/
S(1), 172.23(4)8), this dis-
tortion being due to the cis arrangement of both phPSꢂ
ligands around the metal. In all other respects the bonds
distances and angles are similar to those found for the
trans isomer [18]. According to these observation we
believe that this compound could have been produced
by a route similar to that depicted in Scheme 2.
Since formation of 4 from the tin(IV) complexes is
irrespective of the R group we decided to carry out
further experiments with only the metalloligand contain-
ing RꢀPh (1). Thus, by reacting [Pt(Cl)2(NCC6H5)2]
/
with complex (1) the same behaviour was observed as
that for the palladium analogue. As in the case of
palladium the more valuable information was obtained
from the 31P-NMR spectrum showing a single signal due
2
It is noteworthy that the trans isomer of 4 was obtained by a
dealkylation reaction (Menschutkin Reaction) using amines of the
phosphino-thioether complex trans-[Pd(Ph2PC6H4-2-SMe)2](BF4)2
[18].
to the presence of the cis isomer at dꢀ
/
ꢂ42.94 ppm
/

D. Canseco-Gonza´lez et al. / Journal of Organometallic Chemistry 679 (2003) 101Á
/109
105
Fig. 1. An ORTEP representation of the structure of [Sn(n Bu)2(Ph2PC6H4-2-S)2] (2) at 50% of probability showing the atom labeling scheme. Selected
˚
bond lengths (A): Sn(1)Ã
/
C(1) 2.141(10), Sn(1)Ã
/
S(1) 2.473(3). Bond angles (8): C(1)Ã
/
Sn(1)Ã
/
C(1)#1 132.8(6), C(1)Ã
/
Sn(1)Ã
/
S(2)#1 106.7(3), C(1)#1Ã
/
Sn(1)Ã
/
S(1)#1 105.3(3), C(1)Ã
/
Sn(1)ÃS(1) 105.3(3), C(1)#1Ã
/
/
Sn(1)ÃS(1) 106.7(3), S(1)#1Ã
/
/
Sn(1)Ã
/S(1) 92.90(13).
(JPÃPt
ꢀ
/
2680 Hz). Crystals of 5 suitable for X-ray
identity of the complex and its conformation was
unequivocally determined to be cis-[Pt(Ph2PC6H4-2-
S)2] (Fig. 3). The crystal structure shows the Pt center
diffraction analysis were obtained from a double layer
system CH2Cl2/MeOH as yellow prisms, thus the
Fig. 2. An ORTEP representation of the structure of cis-[Pd(Ph2PC6H4-2-S)2] (4) at 50% of probability showing the atom labeling scheme. Selected
˚
bond lengths (A): Pd(1)Ã
100.54(4), P(2)ÃPd(1)ÃS(2) 87.07(4), P(1)Ã
/
P(2) 2.2772(10), Pd(1)Ã
/
P(1) 2.2828(10), Pd(1)Ã
S(2) 171.66(4), P(2)ÃPd(1)Ã
/
S(2) 2.3177(10), Pd(1)Ã
/
S(1) 2.3188(11). Bond angles (8): P(2)Ã
Pd(1)ÃS(1) 87.22(4), S(2)ÃPd(1)ÃS(1) 85.20(4).
/
Pd(1)ÃP(1)
/
/
/
/
Pd(1)Ã
/
/
/
S(1) 172.23(4), P(1)Ã
/
/
/
/

106
D. Canseco-Gonza´lez et al. / Journal of Organometallic Chemistry 679 (2003) 101Á109
/
Fig. 3. An ORTEP representation of the structure of cis-[Pt(Ph2PC6H4-2-S)2] (5) at 50% of probability showing the atom labeling scheme. Selected
˚
bond lengths (A): Pt(1)Ã
/
P(2) 2.265(2), Pt(1)Ã
/
P(1) 2.265(2), Pt(1)Ã
/
S(1) 2.325(2), Pt(1)Ã
/
S(2) 2.327(2). Bond angles (8): P(2)Ã
/
Pt(1)ÃP(1) 100.05(7),
/
P(2)ÃPt(1)ÃS(1) 172.28(7), P(1)Ã
/
/
/
Pt(1)ÃS(1) 87.65(7), P(2)Ã
/
/
Pt(1)ÃS(2) 87.60(8), P(1)Ã
/
/
Pt(1)Ã
/
S(2) 171.73(8), S(1)ÃPt(1)ÃS(2) 84.75(8).
/
/
to be located in a slightly distorted square planar
environment (P(2)ÃPt(1)ÃS(1), 172.28(7)8; P(1)ÃPt(1)Ã
S(2), 171.73(8)8), once again the distortion being due to
the steric hindrance caused by the cis arrangement of
the phPSꢂ ligands around the metal center.
distorted square planar geometry, with the phPSꢂ
ligands being coordinated to the metal center in a trans
fashion. In this case the isomerization process observed
for palladium resulted to be more pronounced, this is
probably due to the fact that the structural preference
energy for the nickel is smaller in comparison to that of
Pd and Pt, therefore the isomerization process occurs
faster, thus leading to the behaviour observed in the 31P-
NMR. In addition, since Ni(II) is considerable smaller
in comparison to Palladium(II) or Platinum(II), it would
be more difficult to allocated both phPSꢂ ligands in a
cis conformation due to steric hindrance. It is also
possible that being the affinity of Ni(II) for the
phosphorus center lower in comparison to that of
Pd(II) and Pt(II) the hemilability process in this
particular case may cause the isomerization process to
be more favored leading to the trans isomer, this in fact
may also justify the different cis/trans ratios observed in
the cases of Ni (1:16 cis:trans ratio) and Pd (1.5:1
cis:trans ratio) where a clear trend can be observed to
the point where no trans isomer is observed for the case
of platinum.
/
/
/
/
A similar procedure was applied for nickel, however
in this case the starting material employed was NiCl2×
/
6H2O, analysis of the green microcrystalline powder
obtained by FABꢁ-MS, elemental analysis and multi-
nuclear NMR revealed the compound to have a similar
formulation
Ã
/
[Ni(Ph2PC6H4-2-S)2]Ã
/
to that of the
palladium and platinum analogues, 31P-NMR analysis
of this sample shows a spectrum where a single signal at
dꢀ42.69 ppm can be clearly distinguished due to the
/
presence of the cis isomer. As is the case for the
palladium complex, the 31P-NMR spectra of this sample
after 24 h standing shows two signals one and the more
intense corresponding to the presence of the trans
isomer (dꢀ
intensity (dꢀ
/
56.45 ppm)3 [19] and another of minor
42.69 ppm) due to the presence of the cis
/
isomer (1:16 cis/trans ratio). Crystals of 6 suitable for X-
ray diffraction analysis were obtained in a similar
manner to those of complexes 4 and 5. The crystal
structure obtained shows the Ni center to be in a slightly
To reinforce our hypothesis that the transmetallation
route it is indeed stereoselective, we carried out reactions
of the starting materials [M(Cl)2(NCC6H5)2] Mꢀ
/Pd, Pt
or NiCl2×6H2O with the phPSH proligand in the
presence of NEt3 as base under the same reaction
conditions, analyses by 31P-NMR indicate that irrespec-
/
3
Analogously to complex 4 complex 6 was also synthesized for the
first time by an S-dealkylation process of trans-[Ni(Ph2PC6H4-2-
SMe)2](BF4)2 [19].

D. Canseco-Gonza´lez et al. / Journal of Organometallic Chemistry 679 (2003) 101Á
/109
107
Scheme 1. Possible coordination modes of the metalloligands [Sn(R)2(Ph2PC6H4-2-S)2].
tively of the metal (Ni, Pd or Pt) the product obtained it
is always that in trans configuration (trans-
results with starting materials of the Group 9 (Vaska’s
type complexes) indicate that the transmetallation
process is driven by the amount of chloride present in
the starting materials. Thus, efforts aimed to evaluate
this hypothesis by varying the amount of chlorides in the
starting materials are currently under investigation in
our group.
[M(Ph2PC6H4-2-S)2] MꢀNi, Pd, Pt), thus probing
/
that the route via transmetallation forces the bis-
chelated products to a cis configuration (kinetic pro-
duct) which in time isomerizes to the trans (thermo-
dynamic product) configured products. It is very likely
that this isomerization process occurs through an
unbindingÁbinding process thus illustrating too the
/
hemilabile properties of the ligand phPSꢂ.
In summary, we have shown that by using the tin(IV)
metalloligands of the type [Sn(R)2(Ph2PC6H4-2-S)2] we
can stereoselectively synthesize through transmetallation
reactions the cis isomers of the complexes
4. Supplementary material
Supplementary data for complex 2, 4 and 5 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-
336033; e-mail deposit@ccdc.cam.ac.uk or www:
http://www.ccdc.cam.ac.uk) quoting the deposition
[M(Ph2PC6H4-2-S)2] MꢀNi, Pd, Pt (Scheme 3).
/
The crystal structure obtained in the case of nickel
does not result in the same conformation (cis) as that
observed for Pd and Pt, however this is probably due
more to the inherent properties of the metal center more
than due to the synthetic route. Moreover, preliminary
/
number CCDC 207947Á207949.
/

108
D. Canseco-Gonza´lez et al. / Journal of Organometallic Chemistry 679 (2003) 101Á109
/
Scheme 2. A proposal of the probable steps involved in the formation of the complexes cis-[M(Ph2PC6H4-2-S)2] MꢀNi, Pd and Pt.
/
Scheme 3.

D. Canseco-Gonza´lez et al. / Journal of Organometallic Chemistry 679 (2003) 101Á
/109
109
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˜
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