Synthesis of [SnPh2(SRF)2] SRF = -SC6F4-4-H, -SC6F5: Reactivity towards group 10 transition metal complexes

Article abstract of DOI:10.1016/j.ica.2006.09.003

The organometallic tin(IV) complexes [SnPh₂(SR^F)₂] SR^F = ^-SC₆F₄-4-H (1), ^-SC₆F₅ (2), were synthesized and their reactivity with [MCl₂(

Full text of DOI:10.1016/j.ica.2006.09.003

Inorganica Chimica Acta 360 (2007) 1651–1660
www.elsevier.com/locate/ica
ꢀ
Synthesis of [SnPh2(SRF)2] SRF = ꢀSC6F4-4-H, SC6F5:
Reactivity towards group 10 transition metal complexes
a
b
a
´
´
´
´
Fabiola Estudiante-Negrete , Rocıo Redon , Simon Hernandez-Ortega ,
a
a,
*
´
Ruben A. Toscano , David Morales-Morales
a
Instituto de Quı´mica, Universidad Nacional Auto´noma de Me´xico, Cd. Universitaria, Circuito Exterior, Coyoaca´n, 04510 Me´xico D.F., Mexico
Centro de Ciencias Aplicadas y Desarrollo Tecnolo´gico (CCADET), UNAM. Cd. Universitaria, Circuito Exterior, Coyoaca´n, 04510 Me´xico D.F., Mexico
b
Received 21 July 2006; received in revised form 31 August 2006; accepted 1 September 2006
Available online 20 September 2006
Abstract
The organometallic tin(IV) complexes [SnPh2(SRF)2] SRF = ꢀSC6F4-4-H (1), ꢀSC6F5 (2), were synthesized and their reactivity with
[MCl2(PPh3)2] M = Ni, Pd and Pt explored. Thus, transmetallation products were obtained affording polymeric [Ni(SRF)(l-SRF)]n,
monomeric cis-[Pt(PPh3)2(SC6F4-4-H)2] (3) and cis-[Pt(PPh3)2(SC6F5)2] (4) and dimeric species [Pd(PPh3)(SC6F4-4-H)(l-SC6F4-4-H)]2
(5) and [Pd(PPh3)(SC6F5)(l-SC6F5)]2 (6) for Ni, Pt and Pd, respectively. The crystal structures of complexes 1, 2, 3, 4 and 6 were
determined.
ꢀ 2006 Elsevier B.V. All rights reserved.
Keywords: Thiolate ligands; Transmetallation; Transition metal complexes; Tin complexes; Crystal structures
1. Introduction
plexes as starting materials and where the transmetallation
process is the rate-determining step [5].
Tin complexes have acquired a raising interest in recent
years due to the applications that these compounds have
found in fields such as medicinal and bioinorganic chemis-
try [1], having an important impact in the design of new
species for therapeutic use in the treatment of different ill-
nesses, including different types of cancer [2]. Tin com-
plexes have also been successfully employed in other
areas of chemistry such as self assembly, molecular recog-
nition and catalysis [3]. In this respect, processes involving
transmetallation reactions as key steps for a particular cat-
alytic reaction have been of considerable interest in recent
years. Being this particularly true for reactions involving
the formation of C–C bonds and of particular interest
the Stille reaction [4] which uses organometallic tin com-
Moreover, thiolate complexes have been used profusely
due the relevance that these ligands have had in the design
of complexes able to mimic the biological functions of
active centers of different metalloenzymes like nitrogenase
[6]. Additionally, given the facility with which thiols can
be tuned both steric and electronically, they have been
widely used as auxiliary ligands [7]. Hence, the presence
of electron-withdrawing groups or substituents with steric
requirements favor the formation of mononuclear com-
plexes rather than the thiolate bridged oligomers, usually
generated by using unencumbered thiols [8]. Moreover,
thiolate complexes are known to undergo chemistry at
the sulfur center, including redox and protonation–depro-
tonation processes a plus to traditional chemistry for these
complexes usually centered on the metal [9]. Thus, follow-
ing our current interest in the synthesis, structural studies
and reactivity of thiolate metal complexes [10], we would
like to report here the synthesis of organometallic tin(IV)
*
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.2006.09.003

1652
F. Estudiante-Negrete et al. / Inorganica Chimica Acta 360 (2007) 1651–1660
complexes with the thiols HSC6F5 and HSC6F4-4-H and
their reactivity towards group 10 transition metal
complexes.
2.3. Synthesis of [SnPh2(SC6F5)2] (2)
To a CH2Cl2 solution (30 mL) of [SnPh2(Cl)2] (100 mg,
0.29 mmol) a solution of [Pb(SC6F5)2] (176 mg, 0.29 mmol)
in CH2Cl2 (50 mL) was slowly added. The resulting solu-
tion was allowed to proceed under stirring for 12 h. After
this time the resulting solution was filtered trough a short
plug of celite and the residue washed twice with CH2Cl2
(30 mL) to afford 166 mg of a microcrystalline white pow-
der. Yield: 85%. M.p. 58–60 ꢁC. RMN-1H (300 MHz,
2. Experimental
2.1. Materials and methods
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-
CDCl3),
d
7.47–7.43 (m, Ph, 10H); RMN-19F{1H}
3
(282 MHz, CDCl3), d ꢀ129.88 (dd, JF ꢀF ¼ 24:00 Hz,
o
m
4JF ꢀF ¼ 7:05 Hz, o-F), ꢀ155.14 (bt, JF ꢀF ¼ 21:20 Hz,
3
o
p
p
m
1
3
4
Magna 750 FT-IR spectrometer as nujol mulls. The H
p-F), ꢀ161.87 (m, JF ꢀF ¼ 23:26 Hz, JF
¼ 7:05 Hz,
mꢀFp
o
m
NMR spectra were recorded on a JEOL GX300 spectrom-
eter. Chemical shifts are reported in ppm down field of
TMS using the solvent (CDCl3, d = 7.27) as internal stan-
dard. 31P{1H}, 19F{1H} and 119Sn{1H} spectra were
recorded with complete proton decoupling and are
reported in ppm using 85% H3PO4, C6F6 or SnMe4 as
external standards, respectively. Elemental analyses were
determined on a Perkin–Elmer 240. Positive-ion FAB mass
spectra were recorded on a JEOL JMS-SX102A mass spec-
trometer operated at an accelerating voltage of 10 kV.
Samples were desorbed from a nitrobenzyl alcohol
(NOBA) matrix using 3 keV xenon atoms. Mass measure-
ments 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. Melting points were deter-
mined in a MEL-TEMP capillary melting point apparatus
and are reported without correction.
m-F); RMN-119Sn{1H} (112 MHz, CDCl3), d 18.09 ppm
(s). Elem. Anal. Calc. for [C24H10F10S2Sn]: C, 42.95; H,
1.50. Found: C, 42.58; H, 1.42%. MS-FAB+ [M+ꢀPh] =
595 m/z.
2.4. Synthesis of cis-[Pt(PPh3)2(SC6F4-4-H)2] (3)
To
a solution of [Sn(Ph)2(SC6F4-4-H)2] (100 mg,
0.156 mmol) in CH2Cl2 (20 mL), a solution of cis-
[Pt(PPh3)2(Cl)2] (123 mg, 0.156 mmol) in CH2Cl2 (20 mL)
was added dropwise under stirring, the resulting yellow-
green solution was allowed to stir overnight, after which
time the pale green precipitate formed was filtered out
and recrystallized from CH2Cl2–hexane, to afford 3 as a
yellow-green microcrystalline powder. 147 mg, Yield:
87%. M.p. 183–185 ꢁC. NMR 1H (300 MHz, CDCl3), d
7.7–7.1 (m, Ph, 32H); NMR 31P{1H} (121 MHz, CDCl3),
1
d 19.12 (s, JP–Pt = 3.1 kHz, P); NMR 19F{1H} (282
3
MHz, CDCl3),
d
ꢀ133.85 (bm, JF ꢀF ¼ 23:97Hz,
o
m
The complex [SnPh2(Cl)2] and the PdCl2, PtCl2, NiCl2
metal salts and thiols HSC6F4-4-H and HSC6F5 were
obtained commercially from Aldrich Chem. Co. Com-
pounds trans-[NiCl2(PPh3)2] [11], trans-[PdCl2(PPh3)2]
[12], cis-[PtCl2(PPh3)2] [13], and [Pb(SRF)2], SRF =
ꢀSC6F5, ꢀSC6F4-4-H [14]. were synthesized according to
the published procedures.
3
5JF ꢀF ¼ 8:04 Hz, o-F), ꢀ142.11 (m, JF ꢀF ¼ 25:10 Hz,
o
m
o
m
5JF ꢀF ¼ 10:43 Hz, JF ꢀF ¼ 10:15 Hz, m-F). Elem. Anal.
4
o
m
o
m
Calc. for [C48H32F8P2PtS2]: C, 53.29; H; 2.98. Found: C,
53.24; H, 2.86%. MS-FAB+ [M+] = 1081 m/z.
2.5. Synthesis of cis-[Pt(PPh3)2(SC6F5)2] (4)
To a solution of [Sn(Ph)2(SC6F5)2] (100 mg, 0.149 mmol)
in CH2Cl2 (20 mL), a solution of cis-[Pt(PPh3)2(Cl)2]
(117 mg, 0.149 mmol) in CH2Cl2 (20 mL) was added drop-
wise under stirring, the resulting yellow-green solution was
allowed to stir overnight, after which time the green precip-
itate formed was filtered out and recrystallized from
CH2Cl2–hexane, to afford 4 as a green-yellow microcrystal-
line powder. 142 mg, Yield: 85%. M.p. 170–172 ꢁC. NMR
1H (300 MHz, CDCl3), d 7.7–7.1 (m, Ph, 30H); NMR
2.2. Synthesis of [SnPh2(SC6F4-4-H)2] (1)
To a CH2Cl2 solution (30 mL) of [SnPh2(Cl)2] (100 mg,
0.29 mmol) a suspension of [Pb(SC6F4-4-H)2] (165 mg,
0.29 mmol) in CH2Cl2 (50 mL) was slowly added. The
resulting solution was allowed to proceed under stirring
for 12 h. After this time the resulting solution was filtered
trough a short plug of celite and the residue washed twice
with CH2Cl2 (30 mL) to afford 164 mg of a microcrystalline
white powder. Yield: 89%. M.p. 73–75 ꢁC. RMN-1H
(300 MHz, CDCl3), d 7.49–7.40 (m, Ph, 10H), 6.80–6.74
(m, SC6F4-4-H, 2H); RMN-19F{1H} (282 MHz, CDCl3),
d ꢀ129.37 (m, o-F), ꢀ137.76 (m, m-F); RMN-119Sn{1H}
(112 MHz, CDCl3), d 13.81 ppm (s). Elemental Anal. Calc.
for [C24H12F8S2Sn]: C, 45.38; H, 1.90. Found: C, 45.25; H,
1.83%. MS-FAB+ [M+] = 635 m/z.
1
31P{1H} (121 MHz, CDCl3), d 18.85 (s, JP–Pt = 3.1 kHz,
P); NMR 19F{1H} (282 MHz, CDCl3), d ꢀ133.65 (dd,
4
3JF ꢀF ¼ 26:22 Hz, JF ꢀF ¼ 6:20 Hz, o-F), ꢀ161.98 (bt,
o
m
o
p
4JF ꢀF ¼ 23:69 Hz, p-F), ꢀ164.88 (m, JF ꢀF ¼ 23:62 Hz,
3
o
p
o
m
4JF ꢀF ¼ 7:19 Hz, m-F). Elem. Anal. Calc. for
o
p
[C48H30F10P2PtS2]: C, 51.57; H, 2.70. Found: C, 51.48; H,
2.68%. MS-FAB+ [M+] = 1117 m/z.

F. Estudiante-Negrete et al. / Inorganica Chimica Acta 360 (2007) 1651–1660
1653
2.6. Synthesis of [Pd(PPh3)(SC6F4-4-H)(l-SC6F4-4-H)]2
(5)
tered and the solvent removed under vacuum. The residue
was recrystallized from CH2Cl2–hexane, to afford 6 as a
red microcrystalline powder. 203 mg, Yield: 89%. M.p.
1
To
a
solution of [Sn(Ph)2(SC6F4-4-H)2] (100 mg,
264–265 ꢁC. NMR H (300 MHz, CDCl3, 330 K), d 7.7–
0.156 mmol) in CH2Cl2 (20 mL), a solution of trans-
[Pd(PPh3)2(Cl)2] (109 mg, 0.156 mmol) in CH2Cl2 (20 mL)
was added dropwise under stirring, the resulting yellow-
orange solution was allowed to stir overnight, after this
time the solution was filtered and the solvent removed
under vacuum. The residue was recrystallized from
CH2Cl2–hexane, to afford 5 as an orange microcrystalline
powder. 196 mg, Yield: 85%. M.p. 182–183 ꢁC. Elem. Anal.
Calc. for [C60H34F16P2Pd2S4]: C, 49.29; H, 2.34. Found: C,
49.15; H, 2.28%. MS-FAB+ [M+ꢀSC6F4-4-H] = 1381 m/z.
7.1 (m, Ph, 30H); NMR 31P{1H} (121 MHz, CDCl3,
330 K), d 28.2 (s, P); NMR 19F{1H} (282 MHz, CDCl3,
330 K), d ꢀ126.2 (bm, o-F bridge), ꢀ131.3 (m, o-F terminal),
ꢀ148.0 (m, p-F bridge), ꢀ155.5 (m, p-F terminal), ꢀ159.6
(m, m-F bridge), ꢀ163.5 (m, m-F terminal). Elem. Anal.
Calc. for [C60H30F20P2Pd2S4]: C, 46.98; H, 1.97. Found: C,
46.51; H, 2.01%. MS-FAB+ [M+ꢀSC6F5] = 1335 m/z.
2.8. Data collection and refinement for [SnPh2(SC6F4-4-
H)2] (1), [SnPh2(SC6F5)2](2), cis-[Pt(PPh3)2(SC6F4-4-
H)2] (3), cis-[Pt(PPh3)2(SC6F5)2] (4),
2.7. Synthesis of [Pd(PPh3)(SC6F5)(l-SC6F5)]2 (6)
[Pd(PPh3)(SC6F5)(l-SC6F5)]2 (6)
To a solution of [Sn(Ph)2(SC6F5)2] (100 mg, 0.149 mmol)
in CH2Cl2 (20 mL), a solution of trans-[Pd(PPh3)2(Cl)2]
(104 mg, 0.149 mmol) in CH2Cl2 (20 mL) was added drop-
wise under stirring, the resulting red-orange solution was
allowed to stir overnight, after this time the solution was fil-
Crystalline colorless prisms of 1 and 2, yellow prisms of
3 and 4 and a reddish prism of 5 grown independently from
CH2Cl2/MeOH solvent systems were glued each to glass
fibers. The X-ray intensity data were measured at 291 K
for 1, 2 and 3 and at 293 K for 4 and 6 on a Bruker
Table 1
Summary of crystal structure data for [SnPh2(SC6F4-4-H)2] (1), [SnPh2(SC6F5)2] (2) cis-[Pt(PPh3)2(SC6F4-4-H)2] (3), cis-[Pt(PPh3)2(SC6F5)2] (4),
[Pd(PPh3)(SC6F5)(l-SC6F5)]2 (6)
Compound
[SnPh2(SC6F4-4-H)2] (1) [SnPh2(SC6F5)2] (2) cis-[Pt(PPh3)2-
(SC6F4-4-H)2] (3)
cis-[Pt(PPh3)2-
(SC6F5)2] (4)
[Pd(PPh3)(SC6F5)(l-SC6F5)]2 (6)
Empirical formula
Formula weight
Temperature (K)
Crystal system
C
635.15
291(2)
monoclinic
P21/c
24H12F8S2Sn
C24H10F10S2Sn
671.13
291(2)
C49H32Cl2F8P2PtS2 C49H32F10OP2PtS2
C61H31C13F20P2Pd2S4
1653.19
293(2)
monoclinic
P21/c
1164.80
291(2)
1135.89
293(2)
triclinic
monoclinic
P21/n
monoclinic
C2/c
ꢀ
Space group
P1
Crystal size (mm)
Unit cell dimensions
0.26 · 0.22 · 0.04
0.32 · 0.26 · 0.22
0.30 · 0.14 · 0.12
0.406 · 0.128 · 0.036 0.178 · 0.178 · 0.158
˚
a (A)
11.9083(7)
7.3992(4)
27.345(2)
90
90.011(1)
90
9.5051(6)
10.6793(6)
12.6904(7)
82.128(1)
73.950(1)
74.022(1)
1187.55(12)
2
14.8746(8)
19.602(1)
17.5800(9)
90
94.691(1)
90ꢁ
31.816(2)
13.9880(8)
20.419(1)
90
90.626(1)
90
10.0622(5)
17.5843(9)
19.270(1)
90
99.209(1)
90
˚
b (A)
˚
c (A)
a (ꢁ)
b (ꢁ)
c (ꢁ)
3
˚
Volume (A )
2409.4(2)
4
5108.8(5)
4
9086.8(9)
8
3365.6(3)
2
Z
Density (g/cm3)
h Range for data
collection (ꢁ)
Reflections collected
Independent
1.751
1.71–25.00
1.877
2.30–25.00
1.514
1.56–25.00
1.661
1.28–25.05
1.631
1.58–25.00
18990
4247 [0.0470]
9810
4184 [0.0272]
41500
9003 [0.0492]
36763
8041 [0.0711]
27257
5913 [0.0738]
reflections [Rint
]
F(000)
1240
652
2288
4464
1628
Absorption
correction
analytical
analytical
analytical
analytical
analytical
Goodness-of-fit on F2 0.986
1.006
0.883
0.985
0.992
R indices (all data)
R1 = 0.0726,
R1 = 0.0294,
wR2 = 0.0638
R1 = 0.0263,
wR2 = 0.0627
4184/0/334
R1 = 0.0438,
wR2 = 0.0667
R1 = 0.0302,
wR2 = 0.0645
9003/0/570
R1 = 0.0703,
wR2 = 0.1120
R1 = 0.0432,
wR2 = 0.0981
8041/0/584
R1 = 0.1009,
wR2 = 0.2429
R1 = 0.0767,
wR2 = 0.2224
5913/0/417
wR2 = 0.0978
R1 = 0.0479,
wR2 = 0.0919
4247/0/316
Final R indices
[I > 2r(I)]
Data/restrains/
parameters
Index ranges
ꢀ14 6 k 6 14,
ꢀ8 6 h 6 8,
ꢀ11 6 k 6 11,
ꢀ12 6 h 6 12,
ꢀ15 6 l 6 15
ꢀ17 6 k 6 17,
ꢀ23 6 h 6 23,
ꢀ20 6 l 6 20
ꢀ37 6 k 6 37,
ꢀ16 6 h 6 16,
ꢀ24 6 l 6 24
ꢀ11 6 k 6 11,
ꢀ20 6 h 6 20,
ꢀ22 6 l 6 22
ꢀ32 6 l 6 32

1654
F. Estudiante-Negrete et al. / Inorganica Chimica Acta 360 (2007) 1651–1660
SMART APEX CCD-based X-ray diffractometer system
equipped with a Mo-target X-ray tube (k = 0.71073 A).
erson method using SHELXS-97 [15] program. The remaining
atoms were located via a few cycles of least squares refine-
ments and difference Fourier maps, using the space groups
˚
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 0.3 ꢁ in x and an exposure time
of 10 s/frame. 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
monoclinic unit cell for 1, 3, 4 and 6 or a triclinic unit cell
for 2 to yield a total of 18990 (1) 9810 (2) 41500 (3) 36763
(4) and 27257 (6) reflections, respectively to a maximum 2h
ꢀ
P21/c with Z = 4 (1), P1 with Z = 2 (2), P21/n with Z = 4
(3), C2/c with Z = 8 (4) and P21/c with Z = 2 (6), respec-
tively. 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 Ueq = 1.2 A to prece-
dent atom. The final cycle of refinement was carried out
using SHELXL-97 [16] and anisotropic thermal parameters
for all non-hydrogen atoms. The details of the structure
determinations are given in Table 1 and selected bond
˚
angle of 50.00ꢁ (0.93 A resolution), of which 4247 (1) 4184
(2) 9003 (3) 8041 (4) and 5913 (6) were independent. Anal-
ysis of the data showed in the three cases negligible decays
during data collection. The structures were solved by Patt-
˚
lengths (A) and angles (ꢁ) and the numbering of the atoms
is shown in Figs. 1 and 3–6, respectively (ORTEP) [17].
˚
Fig. 1. An ORTEP representation of the structure of [SnPh2(SC6F4-4-H)2] (1) at 50% of probability showing the atom labeling scheme. Bond lengths (A):
Sn(1)–C(1) 2.104(5), Sn(1)–C(7) 2.110(6), Sn(1)–S(1) 2.4223(17), Sn(1)–S(2) 2.4231(15). Bond angles (ꢁ): C(1)–Sn(1)–C(7) 117.79(19), C(1)–Sn(1)–S(1)
104.56(15), C(7)–Sn(1)–S(1) 111.43(19), C(1)–Sn(1)–S(2) 107.10(14), C(7)–Sn(1)–S(2) 108.86(17), S(1)–Sn(1)–S(2) 106.44(6).
Fig. 2. X-SEED [28] representation of the intramolecular and intermolecular p–p stacking interactions observed in complex [SnPh2(SC6F4-4-H)2] (1).

F. Estudiante-Negrete et al. / Inorganica Chimica Acta 360 (2007) 1651–1660
1655
˚
Fig. 3. An ORTEP representation of the structure of [SnPh2(SC6F5)2] (2) at 50% of probability showing the atom labeling scheme. Bond lengths (A):
Sn(1)–C(7) 2.128(2), Sn(1)–C(1) 2.130(2), Sn(1)–S(2) 2.4329(8), Sn(1)–S(1) 2.4331(7). Bond angles (ꢁ): C(7)–Sn(1)–C(1) 112.63(10), C(7)–Sn(1)–S(2)
114.66(7), C(1)–Sn(1)–S(2) 104.11(7), C(7)–Sn(1)–S(1) 110.85(7), C(1)–Sn(1)–S(1) 109.92(7), S(2)–Sn(1)–S(1) 104.14(3).
Fig. 4. An ORTEP representation of the structure of cis-[Pt(PPh3)2(SC6F4-4-H)] (3) at 50% of probability showing the atom labeling scheme. Bond
˚
lengths (A): Pt(1)–P(1) 2.2806(11), Pt(1)–P(2) 2.2969(11), Pt(1)–S(2) 2.3621(11), Pt(1)–S(1) 2.3733(11). Bond angles (ꢁ): P(1)–Pt(1)–P(2) 96.54(4), P(1)–
Pt(1)–S(2) 87.05(4), P(2)–Pt(1)–S(2) 171.07(4), P(1)–Pt(1)–S(1) 177.04(4), P(2)–Pt(1)–S(1) 84.65(4), S(2)–Pt(1)–S(1) 92.17(4)
3. Results and discussion
tion of complexes [SnPh2(SC6F4-4-H)2] (1) and
[SnPh2(SC6F5)2] (2) in good yields (Scheme 1). Analysis
of both complexes by H NMR reveals the presence of
1
The reaction in an 1:1 molar ratio of [SnPh2(Cl)2] and
[Pb(SC6F4-4-H)2] or [Pb(SC6F5)2] resulted on the forma-
the phenyl substituents with signals in the typical region

1656
F. Estudiante-Negrete et al. / Inorganica Chimica Acta 360 (2007) 1651–1660
˚
Fig. 5. An ORTEP representation of the structure of cis-[Pt(PPh3)2(SC6F5)] (4) at 50% of probability showing the atom labeling scheme. Bond lengths (A):
Pt(1)–P(1) 2.282(2), Pt(1)–P(2) 2.297(2), Pt(1)–S(2) 2.344(2), Pt(1)–S(1) 2.372(2). Bond angles (ꢁ): P(1)–Pt(1)–P(2) 96.31(7), P(1)–Pt(1)–S(2) 85.90(8), P(2)–
Pt(1)–S(2) 174.21(8), P(1)–Pt(1)–S(1) 177.03(7), P(2)–Pt(1)–S(1) 85.38(7), S(2)–Pt(1)–S(1) 92.65(8).
Fig. 6. An ORTEP representation of the structure of [Pd(PPh3)(SC6F5)(l-SC6F5)]2 (6) at 50% of probability showing the atom labeling scheme. Bond
˚
lengths (A): Pd(1)–P(1) 2.286(2), Pd(1)–S(2) 2.306(2), Pd(1)–S(1)#1 2.365(2), Pd(1)–S(1) 2.381(2), S(1)–Pd(1)#1 2.365(2). Bond angles (ꢁ): P(1)–Pd(1)–S(2)
87.90(8), P(1)–Pd(1)–S(1)#1 95.28(7), S(2)–Pd(1)–S(1)#1 176.67(8), P(1)–Pd(1)–S(1) 176.90(8), S(2)–Pd(1)–S(1) 95.20(8), S(1)#1–Pd(1)–S(1) 81.63(7),
Pd(1)#1–S(1)–Pd(1) 98.37(7).
1
for aromatic protons, additionally the H NMR spectrum
of complex 1 exhibits a multiplet centered at 6.77 ppm
due to the aromatic protons in the para position of the thi-
olates in ꢀSC6F4-4-H, the fact that we are observing only a
single signal for these protons clearly indicates magnetic
equivalence of the two ꢀSC6F4-4-H substituents. Further

F. Estudiante-Negrete et al. / Inorganica Chimica Acta 360 (2007) 1651–1660
1657
R
F
F
F
F
F
Cl
F
Pb(SC6F4-4-R)2
acetone
F
R
F
S
+
PbCl2
Sn
Cl
Sn
S
R = H(1), F(2)
Scheme 1. Synthesis of the [SnPh2(SRF)2] SRF
=
ꢀSC6F4-4-H (1) and ꢀSC6F5 (2) complexes.
analysis of complex 1 by 19F{1H} shows signals due to the
fluorinated ligands ꢀSC6F4-4-H with multiplets at ꢀ129.37
and ꢀ137.76 ppm due to the fluorines in the ortho and meta
positions, respectively. A similar behavior is observed for
complex 2 where signals due to the ortho, para and meta
fluorines in ꢀSC6F5 are observed at ꢀ129.88, ꢀ155.14
and ꢀ161.87 ppm, respectively. Interestingly, analysis by
119Sn{1H} NMR reveal the electron-withdrawing effect of
the fluorinated substituents over the tin center, thus single
signals due to the unique tin centers in complexes 1 and 2
are observed at 13.81 and 18.09 ppm, respectively exhibit-
ing the more pronounced electron-withdrawing effect of
the ligand ꢀSC6F5. Analysis by FAB+-MS shows peaks
at 635 and 595 m/z due the molecular ion of complex 1
and the molecular ion less a phenyl group for 2, respec-
tively. Elemental analyses on both cases are in agreement
with the proposed formulations.
stoichiometric reactions of [SnPh2(SC6F4-4-H)2] (1) and
[SnPh2(SC6F5)2] (2) with cis-[Pt(PPh3)2(Cl)2] afforded the
complexes cis-[Pt(PPh3)2(SC6F4-4-H)] (3) and cis-
[Pt(PPh3)2(SC6F5)2] (4) in good yields. Analysis of these
1
products by H NMR exhibit in both cases signals in the
aromatic region due to the phenyl groups present in the
molecules and analogously to complex 1, the spectra of
complex 3 shows a multiplet centered in 6.62 ppm that evi-
dences the presence of the para proton in the ꢀSC6F4-4-H
group. The 31P{1H} NMR experiments for the two com-
plexes show unique signals flanked by their corresponding
satellites at 19.12 and 18.85 ppm for 3 and 4, respectively
1
with coupling constant values of JP–Pt equal to 3.1 kHz
in both cases, these data being in agreement with both
phosphorus being magnetically equivalent and arranged
in a cis conformation [19]. Evidence obtained from the
analysis of both complexes by 19F{1H} NMR exhibits the
presence of the fluorinated fragments, with signals
observed at ꢀ133.85 and ꢀ142.11 ppm for the ortho and
meta fluorine atoms of the ꢀSC6F4-4-H ligand in 3 and
multiplets at ꢀ133.65, ꢀ161.98 and ꢀ164.88 for the ortho,
meta and para fluorines in the ꢀSC6F5 ligands for complex
4. Additionally, analysis by FAB+-MS shows in both cases
the molecular ion at 1081 and 1117 m/z for 3 and 4, respec-
tively. Furthermore, results obtained from elemental anal-
ysis of the two complexes are also in agreement with the
proposed formulations.
For the two complexes, cis-[Pt(PPh3)2(SC6F4-4-H)2] (3)
(Fig. 4) and cis-[Pt(PPh3)2(SC6F5)2] (4), (Fig. 5) we were
able to obtain single crystals suitable for their X-ray dif-
fraction analysis, the structures obtained confirm unequiv-
ocally the cis arrangement assumed above from the NMR
data, showing both platinum centers into slightly distorted
square planar environments having the two triphenylphos-
phines in a cis arrangement and completing the coordina-
tion the two thiolate ligands also allocated in a cis
arrangement around the metal. In both cases, the bond dis-
tances and angles are within the expect values [20]. It is
noteworthy that the number of structurally analyzed com-
pounds 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 [21,22], P–P ligands [23], or both types
[21,24] were used allowing exclusively cis arrangement and
Crystals suitable for single crystal X-diffraction analysis
were obtained for both complexes. Given the structural
similitude of these complexes they share also a number of
common features, thus both tin centers are located into
slightly distorted tetrahedral environments. The Sn–S dis-
tances Sn(1)–S(1) 2.4223 (17) and Sn(2)–S(2) 2.4231 (15)
in complex 1 (Fig. 1) are slightly shorter than those found
in complex 2 (Fig. 3). A closer analysis of the crystal struc-
ture of complex [SnPh2(SC6F4-4-H)2] (1) reveals two p–p
stacking interactions in the crystal [18], one intermolecular
between the ꢀSC6F4H and one –C6H5 ring and the other
intramolecular between the ꢀSC6F4H rings of two mole-
cules (Fig. 2). The p–p intermolecular interactions is given
between the C1–C6 and C19–C24 aromatic rings, the angle
between the rings is 18ꢁ, and the centroid–centroid distance
˚
is 3.789(4) A, the perpendicular distance between the rings
˚
is between 3.49 and 3.57 A. The C13–C18 ring interacts
with the C13–C18 ring of a molecule at, 1 ꢀ x, 1 ꢀ y, ꢀz;
the rings are parallel with centroid–centroid distance of
˚
˚
3.522(3) A and a perpendicular distance of 3.49 A. This
stacking interactions seem to reduce the angle S(2)–Sn–
C(1) (107.10(4) versus 110.85(7) in 2), it is also probable
that as result of these stacking interactions observed for
complex 1, the bond distances would also be affected thus
having as ultimate consequence their shortening (Fig. 2).
With these complexes in hand, reactions using group 10
transition metal starting materials were attempted. Thus,

1658
F. Estudiante-Negrete et al. / Inorganica Chimica Acta 360 (2007) 1651–1660
RF
RF
Cl
Sn
Cl
Cl
PPh3
Cl
S
S
S
PPh3
PPh3
Ph
Ph
Ph
Ph
Pt
Sn
RF
Pt
Ph3P
S
RF
RF
S
S
PPh3
PPh3
Pt
RF
Scheme 2. A proposal of the probable steps involved in the formation of the complexes cis-[Pt(PPh3)2(SRF)2].
at the same time avoiding the very well known polymeriza-
tion of these complexes. Thus, examples of motifs with
exclusively mono-dentate S and P ligands in a cis arrange-
ment are rare [25].
this complex at the same temperature exhibits two signals
at 28.27 and 28.11 ppm, these signals being probably due
to the syn and anti isomers for the molecule. Additionally,
analysis of both complexes by FAB+-MS shows peaks corre-
sponding to the molecular ion less one thiolate fragment at
1381 m/z [M+ꢀSC6F4-4-H] for compound 5 and at
1335 m/z [M+ꢀSC6F5] for complex 6. This information
and that obtained from the elemental analyses agrees in both
cases with the proposed formulations.
It is possible that the formation of these complexes may
proceed via a transmetallation reaction (Scheme 2), thus
promoting the formation of the cis isomer exclusively.
Analogous experiments using the palladium starting
material trans-[Pd(PPh3)2(Cl)2] with stoichiometric amounts
of complexes [SnPh2(SC6F4-4-H)2] (1) and [SnPh2(SC6F5)2]
(2) afforded compounds [Pd(PPh3)(SC6F4-4-H)(l-SC6F4-4-
H)]2 (5) and [Pd(PPh3)(SC6F5)(l-SC6F5)]2 (6) in good yields.
In both cases analysis by 1H NMR revealed the presence of
aromatic protons, and as is for the case of complexes 1 and
3 signals due to the presence of the para proton in the
ꢀSC6F4-4-H group are observed for complex 5. However
Crystals of 6 suitable for single crystal X-ray diffraction
analysis were obtained by slow diffusion of methanol on a
saturated solution of 6 in dichloromethane. The structure
obtained shows a dimeric palladium compound (Fig. 6) with
the two palladium centers located into slightly distorted
square planar environments and bridged by two ꢀSC6F5
thiolate ligands, the coordination of the palladiums is com-
pleted by one terminal thiolate ꢀSC6F5 and one PPh3
ligands. Both the bridge and terminal thiolates are arranged
in an anti conformation and the PPh3 ligands are arranged
in a mutually trans conformation. The bond distances and
angles are typical and comparable to those observed in sim-
ilar bimetallic structures [27]. These results clearly show that
the proposed structures for complexes 5 and 6 are indeed
dimeric. The fact that in the case of palladium bimetallic
species were obtained is due to the inherent properties of this
metal, that along the periodic table (Ni, Pd and Pt) the pro-
pensity of these group of metals to polymerize increases
from Pt to Ni, this fact may also explain the decomposition
(polymerization) of complex [Pd(PPh3)(SC6F4-4-H)(l-
SC6F4-4-H)]2 (5) in solution, since the thiolate ꢀSC6F4-4-
H is not big enough nor electron-withdrawn enough to
avoid the polymerization via the sulfur atom, thus generat-
ing insoluble polymers after prolonged times in solution,
probably due to the loss of the PPh3 ligands. This fact
may also account for the results obtained when analogous
reactions carried out using the nickel starting material
trans-[Ni(PPh3)2(Cl)2] afforded in both cases green insoluble
powders, these polymeric species were not further analyzed.
In summary, we have shown that by using the tin(IV)
thiolate complexes of the type [SnPh2(SRF)2]SRF =
ꢀSC6F5 (1), ꢀSC6F4-4-H (2) we can stereoselectively syn-
1
in these cases the H NMR spectra are more complicated,
exhibiting a considerable number of signals indicative of a
probable dynamic equilibrium. These results were expected
given the proposed formulations for the dimeric species
obtained, where the sulfur inversion process may lead to
the observation in the NMR time scale of the different prob-
able isomers in solution, i.e. syn, anti, etc. [26]. Thus, VT
NMR experiments were performed with the aim of attain
clear information to identifying the probable structure of
the complexes 5 and 6, thus 19F{1H} NMR were collected
at temperatures as low as 205 K in CDCl3, however even at
these temperatures the coalescence of signals was not
reached and the interpretation of the NMR spectra resulted
difficult, additionally it was noted that complex 5 was unsta-
ble in solution progressively given place the initially red-
orange solution to an insoluble dark orange precipitate.
Thus, experiments carried out at higher temperatures were
performed only with complex 6. Hence experiments at
330 K afforded an 19F{1H} NMR spectra were six signals
(multiplets) can be clearly identified, two corresponding to
the ortho-fluorines at ꢀ126.2 (bridge) and ꢀ131.3 (terminal)
ppm, two more due to the fluorines in the para positions at
ꢀ148.0 (bridge) and ꢀ155.5 (terminal) ppm and finally two
more signals due to the meta-fluorines at ꢀ159.6 (bridge)
and ꢀ163.5 (terminal) ppm. 31P{1H} NMR experiments of

F. Estudiante-Negrete et al. / Inorganica Chimica Acta 360 (2007) 1651–1660
1659
RF
*
*
S
*
Ni
Ni
S
RF
*
n
trans-[NiCl2(PPh3)2]
SC6F5,
SC6F4-4-H
SRF=
RF
S
Sn
RF
S
cis-[PtCl2(PPh3)2]
PPh3
trans-[PdCl2(PPh3)2]
RF
RF
RF
S
S
S
PPh3
Pt
Pd
Pd
RF S
PPh3
RF
S
Ph3P
S
RF
Scheme 3.
thesize through transmetallation reactions the cis isomers
of the complexes cis-[Pt(PPh3)2(SC6F4-4-H)] (3) and cis-
[Pt(PPh3)2(SC6F5)2] (4) in good yields, it is probable that
similar species are formed when the palladium starting
material trans-[Pd(PPh3)2(Cl)2] is employed, however in
this case the formation of dimeric species is observed driven
by the intrinsic properties of the metal and the steric and
electronic properties of the fluorinated thiolates employed
in these reactions, by the same arguments polymeric species
are obtained when the nickel starting material trans-
[Ni(PPh3)2(Cl)2] is reacted with the tin(IV)-fluorinated
thiolate complexes 1 and 2 (Scheme 3).
of the FAB+-mass, IR and 19F{1H} spectra, respectively.
The support of this research by CONACYT (J41206-Q,
J43116-F) and PAPIIT (IN114605, IN106405) is gratefully
´
´
acknowledged. We are indebted to Dr. Jesus Valdes-Martı-
nez, for its invaluable help in the discussion of the p–p
stacking interaction in complex 1.
References
[1] S. Tabassum, C. Pettinari, J. Organomet. Chem. 691 (2006) 1761.
[2] (a) T. Maher, J. Snyder, P. Durham, N.N. Gerasimchuk, in:
Proceedings of the 229th ACS National Meeting, San Diego, CA,
United States, March 13–17 (2005) INOR-719 (Abstracts);
(b) M. Gielen, J. Braz. Chem. Soc. 14 (2003) 870, and references
therein;
4. Supplementary material
(c) C.T. Chasapis, S.K. Hadjikakou, A. Garoufis, N. Hadjiliadis, T.
Bakas, M. Kubicki, Y. Ming, Bioinorg. Chem. Appl. 2 (2004) 43;
(d) N. Hoeti, D.E. Zhu, Z. Song, Z. Wu, S. Tabassum, M. Wu, J.
Pharmacol. Exp. Ther. 311 (2004) 22;
(e) N. Hoeti, J. Ma, S. Tabassum, Y. Wang, M. Wu, J. Biochem. 134
(2003) 521;
(f) N.M. Xanthopoulou, S.K. Hadjikakou, N. Hadjiliadis, M.
Schurmann, K. Jurkschat, A. Michaelides, S. Skoulika, T. Bakas, J.
Binolis, S. Karkabounas, K. Charalabopoulos, J. Inorg. Biochem. 96
(2003) 425.
CCDC 614100, 614101, 614102, 614103, and 614104
contain the supplementary crystallographic data for 1, 2,
3, 4, and 6. 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.
[3] (a) A.P. Dove, V.C. Gibson, E.L. Marshall, A.J.P. White, D.J.
Williams, Chem. Commun. (2001) 283;
Acknowledgements
(b) N. Nimitsiriwat, E.L. Marshall, V.C. Gibson, M.R.J. Elsegood,
S.H. Dale, J. Am. Chem. Soc. 126 (2004) 13598;
(c) J.L. Faure, H. Gornitzka, R. Reau, D. Stalke, G. Bertrand, Eur.
J. Inorg. Chem. (1999) 2295;
F.E.-N. thank CONACYT for financial support. We
thank Chem. Eng. Luis Velasco Ibarra, M. Sc. Francisco
´
´
´
´
Javier Perez Flores and Erendira Garcıa Rıos and Ma. de
(d) K.B. Aubrecht, M.A. Hillimyer, W.B. Tolman, Macromolecules
35 (2002) 644;
las Nieves Zavala for their invaluable help in the running

1660
F. Estudiante-Negrete et al. / Inorganica Chimica Acta 360 (2007) 1651–1660
´
(e) R. Garcıa-Zarracino, H. Ho¨pfl, J. Am. Chem. Soc. 127 (2005)
3120.
[17] L.J. Farrugia, J. Appl. Crystallogr. 30 (1997) 565.
[18] (a) T. Dahl, Acta Crystallogr., Sect. B 33 (1997) 3021;
(b) C.J.J. Janiak, J. Chem. Soc., Dalton Trans. (2000) 3885.
[19] L.D. Quin, J.G. Verkade, Phopshorus-31 NMR Spectral Proper-
ties in Compound Characterization and Structural Analysis, Wiley,
1994.
[4] (a) D. Milstein, J.K. Stille, J. Am. Chem. Soc. 101 (1979) 4992;
´
(b) D.J. Cardenas, Angew. Chem., Int. Ed. Engl. 42 (2003) 384;
(c) K. Fugami, M. Kosugi, Organotin Compounds, in: N. Miyaura
(Ed.), Cross Coupling Reactions. A Practical Guide. Topics in
Current Chemistry, vol. 219, Springer, 2002, p. 87.
[5] P. Espinet, A.M. Echavarren, Angew. Chem., Int. Ed. 43 (2004) 4704.
[6] (a) I. Bertini, H.B. Gray, S.J. Lippard, J.S. Valentine, Bioinorganic
Chemistry, University Science Books, USA, 1994 (Chapter 7);
(b) D.H. Nguyen, H.-F. Hsu, M. Millar, S.A. Koch, J. Am. Chem.
Soc. 118 (1996) 8963;
´
`
[20] (a) R. Redon, R. Cramer, S. Bernes, D. Morales, H. Torrens,
Polyhedron 20 (2001) 3119;
´
´
(b) J. Garcıa, E. Martın, D. Morales, H. Torrens, Inorg. Chim. Acta.
207 (1993) 93;
´
(c) R. Redon, H. Torrens, Z. Wang, D. Morales-Morales, J.
Organomet. Chem. 654 (2002) 16;
´
(c) J.D. Niemoth-Anderson, K.A. Clark, T.A. George, C.R. Ross, J.
Am. Chem. Soc. 122 (2000) 3977.
(d) O. Baldovino-Pantaleon, G. Rıos-Moreno, R.A. Toscano, D.
Morales-Morales, J. Organomet. Chem. 690 (2005) 2880;
´
´ ´ ´ ´
(e) C. Herrera-Alvarez, V. Gomez-Benıtez, R. Redon, J.J. Garcıa, S.
[7] (a) L.L. Maisela, A.M. Crouch, J. Darkwa, I.A. Guzei, Polyhedron
20 (2001) 3189;
´
Hernandez-Ortega, R.A. Toscano, D. Morales-Morales, J. Organo-
(b) O. Crespo, F. Canales, M.C. Gimeno, P.G. Jones, A. Laguna,
Organometallics 18 (1999) 3142;
(c) D.-Y. Noh, E.-M. Seo, H.-J. Lee, H.-Y. Jang, M.-G. Choi, Y.H.
Kim, J. Hong, Polyhedron 20 (2001) 1939;
(d) V.D. de Castro, G.M. de Lima, A.O. Porto, H.G.L. Siebald, J.D.
de Souza Filho, J.D. Ardisson, J.D. Ayala, G. Bombieri, Polyhedron
23 (2004) 63;
met. Chem. 689 (2004) 2464.
´
´
´
[21] J. Fornies-Camer, A. Aaliti, N. Ruiz, A.M. Masdeu-Bulto, C. Claver,
C.J. Cardin, J. Organomet. Chem. 530 (1997) 199.
[22] (a) S.A. Bryan, D.M. Roundhill, Acta Crystallogr., Sect. C 39 (1983)
184;
(b) M.J.G. Lesley, W. Clegg, T.B. Marder, N.C. Norman, A.G.
Orpen, A.J. Scott, J. Starbuck, Acta Crystallogr., Sect. C 55 (1999)
1272;
(c) D.S. Dudis, C. King, J.P. Fackler Jr., Inorg. Chim. Acta 181
(1991) 99;
(e) T.F. Baumann, J.W. Sibert, M.M. Olmstead, A.G.M. Barrett,
B.M. Hoffman, J. Am. Chem. Soc. 116 (1994) 2639.
[8] J.R. Dilworth, J. Hu. Adv. Inor. Chem. 40 (1993) 411.
[9] See for instance: (a) J.R. Dilworth, D. Morales, Y. Zheng, J. Chem.
Soc. Dalton. Trans. (2000) 3007;
(d) C.E. Keefer, S.T. Purrington, R.D. Bereman, B.W. Knight, D.R.
Bedgood Jr., P.D. Boyle, Inorg. Chim. Acta. 282 (1998) 200.
´
´
´
(b) V. Gomez-Benıtez, R.A. Toscano, D. Morales-Morales, Inorg.
[23] (a) M. Capdevila, W. Clegg, P. Gonzales-Duarte, B. Harris, I. Mira,
Chem. Commun. (2006), doi:10.1016/j.inoche.2006.08.020.
J. Sola, I.C. Taylor, J. Chem. Soc., Dalton Trans. (1992) 2817;
(b) G. Wei, H. Liu, Acta Crystallogr., Sect. C 46 (1990) 2457.
[24] J.M. Bevilacqua, J.A. Zuleta, R. Eisenberg, Inorg. Chem. 33 (1994)
258.
[25] (a) Q. Chen, F. Boeheim, J. Dabrowiak, J. Zubieta, Inorg. Chim.
Acta. 216 (1994) 83;
´
[10] (a) D. Morales-Morales, R. Redon, Y. Zheng, J.R. Dilworth, Inorg.
Chim. Acta. 328 (2002) 39;
(b) J.R. Dilworth, P. Arnold, D. Morales, Morales Morales, Y.L.
Wong, Y. Zheng, in: The Chemistry and Applications of Complexes
with Sulfur LigandsModern Coordination Chemistry, The Legacy of
Joseph Chatt, Cambridge, UK, 2002, p. 217.
(b) C.E. Briant, G.R. Hughes, P.C. Minshall, D.M.P. Mingos, J.
Organomet. Chem. 202 (1980) C18;
[11] L.M. Venanzi, J. Chem. Soc. (1958) 719.
[12] L. Malatesia, M. Angoletta, J. Chem. Soc. (1957) 1186.
[13] R.D. Gillard, M.F. Pilbrow, J. Chem. Soc. Dalton. (1974) 2320.
[14] M.E. Peach, Can. J. Chem. 46 (1968) 2699.
(c) R. Vicente, J. Ribas, X. Solans, G. Germain, An. Quim. Ser. B. 82
(1986) 47.
´
´
[26] R. Redon, H. Torrens, F.E. Hahn, T. Lugger, S. Hernandez-Ortega,
¨
[15] G.M. Sheldrick, Acta Crystallogr., Sect. A 46 (1990) 467.
[16] SHELXL-97, Program for Crystal Structure Refinement, University of
Go¨ttingen, 1998.
R.A. Toscano, D. Morales-Morales, J. Mol. Struct. 655 (2003) 423.
[27] V.K. Jain, L. Jain, Coord. Chem. Rev. 249 (2005) 3075.
[28] X-Seed program: J.L. Barbour, J. Supramol. Chem. 1 (2001) 189.