Synthesis and molecular structures of platinum and mercury complexes chelated by (phenylthiomethyl)silane ligands

Article abstract of DOI:10.1002/zaac.200400252

Metathesis reaction of the dithioether complex cis-[PtCl ₂{(PhSCH₂)₂SiPh₂}] (2a) with NaBr and NaI yields the square planar complexes cis-[PtX₂{(PhSCH ₂)₂SiPh₂}] (2b, X = Br; 2c, X = I). The new compounds, which are fluxional in solution, have been studied by multinuclear NMR techniques; the crystal structures of 2a-c have been determined by X ray diffraction. This series allows to evaluate the trans-influence of the halide ligands on the lengths of the Pt-S bonds, which increase from 227.26(12) (2a), 228.46(13) (2b) to 229.96(15) (2c) pm due to a more pronounced trans-influence of I compared with Br and Cl. Complexation of (PhSCH₂) ₂SiPh₂ (1a) on HgBr₂ gives the distorted tetrahedral compound [HgBr₂{(PhSCH₂)₂SiPh ₂}] (3), having a quite loose coordination of the ligand both in solution and in the solid state [Hg-S = 291.88(2) pm]. Alternatively, the coordination around Hg may be described as distorted square pyramidal in the solid state, since to due to a weak intermolecular Hg...Br interaction [346.72(13) pm], a dimeric motif is formed. Furthermore, the functionalised cyclic silane (PhSCH₂)₂SiC₄H₆ (1b) has been prepared and co-ordinated as chelating dithioether ligands to [PtCl₂(PhCN)₂] affording the dithioether complex cis-[PtCl₂{(PhSCH₂)₂SiC₄H ₆)}] (4). The crystal structure of 4 has also been determined by an X-ray diffraction study.

Full text of DOI:10.1002/zaac.200400252

Synthesis and Molecular Structures of Platinum and Mercury Complexes
Chelated by (Phenylthiomethyl)silane Ligands
Michael Knorr*, Harmel N. Peindy, and Fabrice Guyon
´
´
´
Besanc¸on/France, Laboratoire de Chimie des Materiaux et Interfaces, Universite de Franche-Comte
Hermann Sachdev
Saarbrücken, Institut für Anorganische Chemie der Universität des Saarlandes
Carsten Strohmann*
Würzburg, Institut für Anorganische Chemie der Universität Würzburg
Received June 29th, 2004.
Dedicated to Professor Michael Veith on the Occasion of his 60th Birthday
Abstract. Metathesis reaction of the dithioether complex cis-
[PtCl2{(PhSCH2)2SiPh2}] (2a) with NaBr and NaI yields the square
planar complexes cis-[PtX2{(PhSCH2)2SiPh2}] (2b, X ϭ Br; 2c,
X ϭ I). The new compounds, which are fluxional in solution, have
been studied by multinuclear NMR techniques; the crystal struc-
tures of 2a-c have been determined by X ray diffraction. This series
allows to evaluate the trans-influence of the halide ligands on the
lengths of the Pt-S bonds, which increase from 227.26(12) (2a),
228.46(13) (2b) to 229.96(15) (2c) pm due to a more pronounced
trans-influence of I compared with Br and Cl. Complexation of
(PhSCH2)2SiPh2 (1a) on HgBr2 gives the distorted tetrahedral com-
pound [HgBr2{(PhSCH2)2SiPh2}] (3), having a quite loose coordi-
nation of the ligand both in solution and in the solid state [Hg-S ϭ
291.88(2) pm]. Alternatively, the coordination around Hg may be
described as distorted square pyramidal in the solid state, since to
due to a weak intermolecular Hg···Br interaction [346.72(13) pm],
a dimeric motif is formed. Furthermore, the functionalised cyclic
silane (PhSCH2)2SiC4H6 (1b) has been prepared and co-ordinated
as chelating dithioether ligands to [PtCl2(PhCN)2] affording the di-
thioether complex cis-[PtCl2{(PhSCH2)2SiC4H6)}] (4). The crystal
structure of 4 has also been determined by an X-ray diffraction
study.
Keywords: Platinum; Mercury; Dithioether complexes; Trans-influ-
ence; Crystal structures; Silicon
Synthese und Molekülstrukturen einiger Dithioether-Platin- und Quecksilberkomplexe
mit chelatisierenden (Phenylthiomethyl)silan-Liganden
Inhaltsübersicht. Die Metathesereaktion des Dithioetherkomplexes
cis-[PtCl2{(PhSCH2)2SiPh2}] (2a) mit NaBr und NaI ergibt die
quadratisch-planaren Komplexe cis-[PtX2{(PhSCH2)2SiPh2}] (2b,
X ϭ Br; 2c, X ϭ I). Die neuen Verbindungen, welche mittels Multi-
kern-NMR untersucht wurden, zeigen dynamisches Verhalten in
Lösung. Die Kristallstrukturen von 2a-c wurden mittels Einkris-
tall-Röntgenstrukuranalyse bestimmt. Diese Serie erlaubt eine
Abschätzung des trans-Einflusses der Halogen- Liganden auf die
Pt-S-Bindungslängen. Diese wachsen von 227.26(12) (2a),
228.46(13) (2b) auf 229.96(15) (2c) pm infolge eines ausgeprägteren
trans-Einflusses von I im Vergleich mit Cl und Br. Koordination
von (PhSCH2)2SiPh2 (1a) an HgBr2 ergibt den verzerrt tetraedri-
schen Komplex [HgBr2{(PhSCH2)2SiPh2}] (3). In dieser Verbin-
dung ist der Ligand sowohl in Lösung als auch im Festkörper ziem-
lich locker gebunden [Hg-S ϭ 291.88(2) pm]. Die Koordination um
das Hg-Atom lässt sich im Festkörper besser als verzerrt quadra-
tisch-pyramidal beschreiben, da infolge einer schwachen inter-
molekularen Hg···Br-Wechselwirkung [346.72(13) pm] ein dimeres
Motiv vorliegt. Weiterhin wurde das funktionalisierte cyclische Si-
lan (PhSCH2)2SiC4H6 (1b) hergestellt und als chelatisierender
Dithioether-Ligand an [PtCl2(PhCN)2] gebunden. Die Kristall-
struktur
des
resultierenden
Dithioether-Komplexes
cis-
[PtCl2{(PhSCH2)2SiC4H6)}] (4) wurde ebenfalls ermittelt.
Introduction
* Prof. Dr. M. Knorr
Faculte des Sciences et des Techniques, 16, Route de Gray, 25030
´
In the past, chelating dithioether ligands RSXnSR have
been used as innocent spectator ligands in coordination
chemistry [1]. However, a growing number of recent papers
deals on the application of dithioether complexes for homo-
geneous catalysis. For example, rhodium(I) complexes lig-
ated by atropisomeric dithioether ligands are catalytically
Besanc¸on, France
E-mail: michael.knorr@univ-fcomte.fr
* Priv.-Doz. Dr. C. Strohmann
Institut für Anorganische Chemie der Universität Würzburg, Am
Hubland, D-97074, Würzburg, Germany
E-mail: c.strohmann@mail.uni-wuerzburg.de
Z. Anorg. Allg. Chem. 2004, 630, 1955Ϫ1961
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1955

M. Knorr, H. N. Peindy, F. Guyon, H. Sachdev, C. Strohmann
active in hydroformylation of styrene, iridium(I) complexes
chelated by 1,4-bis(isopropylthio)butane have been applied
in hydrogenation of olefins [2, 3]. Square-planar PdII dithio-
ether complexes are known to catalyze the alternating co-
polymerization of CO/ tert-butylstyrene [4], other catalytic
applications have been very recently summarized in a review
article [5]. In the context of our interest on the reactivity of
the Pt-alkyl bond towards small insaturated molecules [6],
we have prepared a series of platinum dithioether complexes
of the type cis-[PtX2{(PhSCH2)2SiR2}] (X ϭ hal). These
precursor compounds, chelated with a potentially hemilab-
ile dithioether ligand, may present after alkylation promis-
ing complexes for organometallic chemistry.
perature-dependent coexistence of meso(syn)- and
DL(anti)-isomers was examined by 1H and 195Pt NMR
only in a qualitative manner, since more detailed studies on
this phenomena have been published in the past by other
groups [1]. The presence of meso- and DL-isomers of 2b is
evidenced from the 195Pt{1H} NMR spectrum recorded at
298 K, which displays two broad humps at δ Ϫ2292 and
Ϫ2303. At 323 K the pyramidal inversion is sufficiently
fast, so that only one “averaged planar” conformation is
observed resulting in broadened singlet resonance centred
at δ Ϫ2289 (Figure 2). In the 1H NMR spectrum of 2b
recorded at 298 K, the methylene resonance appears in
form of a very broad resonance at δ 3.01, which sharpens
on progressive heating to give finally (328 K) a sharp singlet
at δ 3.12 with a JPt,H coupling of 56 Hz. In the case of the
iodo-derivative 2c, a broad singulet resonance centered at δ
2.99 is already observable at 298 K.
Figure 2 presents the normalized UV-vis spectra of li-
gand 1a and complex 2c. The superposition shows that
both compounds exibit an intense absorption at 227 nm
3
Results and Discussion
Synthesis of platinum complexes chelated by
diphenylbis[(phenylthio)methyl]silane
In a previous paper we have described the synthesis of cis-
[PtCl2{(PhSCH2)2SiPh2}] (2aЈ) by reaction of diphenylbis-
[(phenylthio)methyl]silane (1a) with [PtCl2(PhCN)2] in
toluene and presented the molecular structure of this com-
pound recorded at 298 K. The pale yellow crystals, ob-
tained by recrystallisation from CH2Cl2, crystallized in the
with
molecular
extinction
coefficients
around
62000 MϪ1cmϪ1. The complex 2c possesses a second low
energy absorption at 258 nm and a third broad, less intense
band at 411 nm with ε 1300 MϪ1cmϪ1, which is absent in 1a.
¯
triclinic space group P1 [7]. However, using CHCl3, as sol-
vent for recrystallisation, orthorhombic crystals of 2a
(space group Pbca) were formed and subjected to an X-ray
diffraction study at 173 K (Fig. 3 and Table 1, see below).
In order to evaluate the trans-influence of halide ligands
situated trans with respect to the thioether groups of com-
plexes of the type cis-[PtX2{(PhSCH2)2SiPh2}] (X ϭ Cl,
Br, I), we reacted 2a with a 10-fold excess of NaBr or NaI
in acetone as solvent. This metathesis reaction afforded the
air stable derivatives cis-[PtBr2{(PhSCH2)2SiPh2}] (2b) and
cis-[PtI2{(PhSCH2)2SiPh2}] (2c), respectively.
As already noticed for 2a, bright yellow 2b also exhibits
dynamic behaviour in solution due to a facile inversion pro-
cess at the sulphur atoms in solution (Scheme 1). This tem-
Fig. 1 195Pt{1H} NMR spectrum of 2b in CDCl3 recorded at 298
and 323 K
Fig. 2 Absorption spectra of 1a and 2c carried out in CH2Cl2
Scheme 1
at 298 K.
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Platinum and Mercury Complexes Chelated by (Phenylthiomethyl)silane Ligands
Crystal structures of 2a-c
Table 1 Selected bond lengths/pm and bond angles/° of 2a-c and 4
Suitable single crystals were grown from CHCl3/heptane
(2a) or CH2Cl2/heptane (2b,c). Figure 3 shows a plati-
num(II) atom in a square planar environment with a cis-
arrangement of the two chloro ligands [Cl(1)-Pt-Cl(2) ϭ
90.11(5)°]. The root mean square deviation from the plane
Pt-S(1)
Pt-S(2)
227.23(12)
227.30(13)
228.61(12)
228.30(14)
230.3(2)
229.61(14)
227.05(12)
226.51(11)
Pt-Cl(1)
Pt-Cl(2)
Pt-Br(1)
Pt-Br(2)
Pt-I(1)
232.58(13)
230.85(12)
230.42(12)
229.16(13)
245.57(7)
243.99(7)
˚
defined by Cl(1)-Cl(2)-Pt-S(1)-S(2) amounts to 0.031 A.
262.64(8)
The six membered Pt-S(1)-S(2)-C(1)-C(2)-Si chelate ring
adopts a distorted chair conformation very similar to that
reported for cis-[PtCl2{PhS(CH2)3SPh}] ligated by a 1,3-bis-
(phenylthio)propane ligand [8]. In contrast to the latter
complex, in which the phenyl substituents of the sulphur
atoms are in an anti-mode with respect to the chelate ring,
the two phenyl groups of 2a are syn-orientated correspond-
ing to a meso-conformation. The Pt-S(1) and Pt-S(2) bond
distances of 227.23(12) and 227.30(13) pm parallel that of
[PtCl2{PhS(CH2)3SPh}] [227.1(2) and 227.4(2) pm]. The av-
eraged Pt-Cl bond length of 2a [231.72(13) pm] is also al-
most equal to that of the 1,3-bis(phenylthio)propane
counterpart [232.50 pm].
Pt-I(2)
260.72(12)
S(1)-C(1)
S(2)-C(2)
S(1)-C(3)
S(2)-C(9)
Si-C(1)
181.0(5)
181.3(5)
177.0(5)
177.5(5)
188.5(5)
188.6(5)
182.9(6)
182.1(6)
178.0(6)
178.2(6)
188.9(6)
189.6(6)
182.8(5)
182.0(6)
179.4(5)
180.8(6)
187.6(5)
188.9(5)
180.8(5)
189.4(5)
178.8(5)
176.9(4)
188.8(4)
119.4(3)
Si-C(2)
Cl(1)-Pt-Cl(2)
Cl(1)-Pt-S(1)
Cl(2)-Pt-S(1)
Cl(1)-Pt-S(2)
Cl(2)-Pt-S(2)
90.11(5)
83.15(5)
172.53(4)
177.32(4)
92.57(5)
88.69(4)
85.87(4)
173.31(4)
177.01(4)
93.51(4)
S(1)-Pt-S(2)
C(1)-Si-C(2)
S(1)-C(1)-Si
S(2)-C(2)-Si
C(1)-S(1)-Pt
C(2)-S(2)-Pt
94.17(4)
107.3(2)
119.4(3)
108.7(2)
112.8(2)
105.6(2)
93.60(5)
108.1(3)
119.4(3)
107.9(3)
113.3(2)
106.3(2)
99.55(6)
109.5(2)
115.9(3)
117.6(3)
112.1(2)
107.1(2)
92.07(4)
108.3(2)
110.4(2)
119.4(3)
109.36(15)
105.5(2)
A view of the square planar molecular structure of the
dibromo derivative 2b, which is isomorphous (orthorhom-
Br(1)-Pt-Br(2)
Br(1)-Pt-S(1)
Br(2)-Pt-S(1)
Br(1)-Pt-S(2)
Br(2)-Pt-S(2)
89.58(3)
83.61(4)
172.46(4)
177.11(4)
93.17(4)
I(1)-Pt-I(2)
I(1)-Pt-S(1)
I(2)-Pt-S(1)
I(1)-Pt-S(2)
I(2)-Pt-S(2)
89.11(4)
86.01(5)
174.26(3)
170.11(3)
85.72(5)
Fig. 3 View of the molecular structure of
cis-[PtCl2{(PhSCH2)2SiPh2}] (2a)
Fig. 5 View of the molecular structure of
cis-[PtI2{(PhSCH2)2SiPh2}] (2c)
bic, space group Pbca) with 2a, is given in Figure 4. Table 1
shows that substitution of the chloro ligands by two bromo
ligands does not affect the most pertinent structural fea-
tures in a significant manner. However, substitution by two
voluminous iodo ligands alters the structural parameters
noticeably. Derivative 2c crystallizes (solvated with two
¯
molecules of CH2Cl2) within the triclinic space group P1.
Fig. 4 View of the molecular structure of
cis-[PtBr2{(PhSCH2)2SiPh2}] (2b)
The coordination around the metal atom (Figure 5) exhibits
Z. Anorg. Allg. Chem. 2004, 630, 1955Ϫ1961
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1957

M. Knorr, H. N. Peindy, F. Guyon, H. Sachdev, C. Strohmann
now a more pronounced deviation from ideal square planar,
the rms deviation fitted through I(1)-I(2)-Pt-S(1)-S(2) being
0.1075 A. In particular the angle I(1)-Pt-S(2) is more acute
Table 2 Selected bond lengths/pm and bond angles/° of 3
˚
Hg-S(1)
288.9(2)
294.7(2)
244.99(10)
244.74(10)
181.1(8)
179.4(8)
177.5(8)
179.3(7)
187.5(8)
189.2(7)
346.72(13)
513.3(2)
Br(1)-Hg-Br(2)
Br(1)-Hg-S(1)
Br(2)-Hg-S(1)
Br(1)-Hg-S(2)
Br(2)-Hg-S(2)
S(1)-Hg-S(2)
C(1)-S(1)-C(3)
S(1)-C(1)-Si
160.39(4)
97.98(5)
100.21(5)
94.69(5)
96.69(5)
76.24(5)
106.4(4)
112.8(4)
117.9(5)
110.7(2)
100.5(3)
91.66(3)
94.98(4)
Hg-S(2)
than the angle Cl(1)-Pt-S(2) of 2a [170.11(3) vs. 177.32(4)°],
whereas the angles I(2)-Pt-S(1) and Cl(1)-Pt-S(2) remain in
a similar range [174.26(3) vs. 172.53(4)°]. The angle S(1)-
Pt-S(2) which is in the case of 2a and 2b about 94°, opens
to 99.55(6)° in the case of 2c. The Pt-S(1) and Pt-S(2) bond
distances of 230.3(2) and 229.61(14) pm are also signifi-
cantly longer than those of 2a. This elongation of the Pt-S
bonds within the series 2a-c is probably due to thermo-
dynamic trans-influence exerted by the halide, which is
known to increase from Cl < Br < I [9]. The comparison
with the literature-known five-membered chelate complexes
cis-[PtX2(PhSCH2CH2SPh)] (X ϭ Cl, Br, I) [10] reveals that
chelatation by a six-membered chelate ring causes a system-
atic lengthening of the average Pt-S bond distances by ca.
3 pm [224.7 vs 227.26(12) 2a], [224.8 vs 228.46(13) 2b] and
226.5 vs. 229.96(15) 2c pm].
Hg-Br(1)
Hg-Br(2)
S(1)-C(1)
S(2)-C(2)
S(1)-C(3)
S(2)-C(9)
Si-C(1)
S(2)-C(2)-Si
Si-C(2)
C(1)-S(1)-Hg
C(2)-S(2)-Hg
Br(1)-Hg-Br(1)#
S(1)-Hg-Br(1)#
Hg-Br(1)#
Hg-Br(2)#
Synthesis of [HgBr2{(PhSCH2)2SiPh2}]
For structural comparison with [PtBr2{(PhSCH2)2SiPh2}]
(2b), we prepared also the analogous mercury complex
[HgBr2{(PhSCH2)2SiPh2}] (3) by reacting HgBr2 with 1a in
toluene. This compound, which crystallizes in form of
stable colourless crystals, displays in the proton NMR spec-
trum a sharp resolved singlet resonance at δ 2.98 due to
the methylene groups. The absence of any noticeable 199Hg
couplings as well a chemical shift close to that of non-coor-
dinated 1a (δ ϭ 2.84) may be indicative for labile coordi-
nation of the dithioether ligand on HgBr2 in solution. Note
that UV-vis, conductivity and molecular weight measure-
ments on addition compounds between aliphatic thioethers
and mercury(II) chloride have evidenced a strong dis-
sociation in solution [11]. More recentlely, Sanger has re-
ported on the facile dissociation of dithioether complexes
of the type [HgCl2{PhS(CH2)nSPh}] (n ϭ 1Ϫ4) in solution
[12]. This hypothesis of a loose bonding of 1a on HgBr2 is
corroborated by the findings of an X-ray diffraction study
performed on single crystals of 3. Figure 6 shows that the
“tetrahedral” coordination around the Hg atom is severely
distorted. The angle Br(1)-Hg-Br(2) [160.39(4)°] is close to
linearity, the angle S(1)-Hg-S(2) [76.24(6)°] deviates also
significantly from tetrahedral (table 2). Despite the soft nat-
ure of mercury, the averaged Hg-S bond distance of 3 is far
longer than that of 2b (291.85 vs. 228.46 pm; atomic radii
Fig. 6 View of the dimeric motif of 3
with averaged bond length of 277.2(5) pm between the thia
donors and the two HgII atoms [17]. The Hg-Br distances of
248.1(3) and 254.0(5) pm of the latter complex are markedly
longer than those of 3 [244.99(10) and 244.74(10) pm], the
angle Br-Hg-Br of 141.55° being closer to tetrahedral than
that of 3. As shown in Figure 6, the Hg center of 3 forms
additionally an intermolecular contact of 346.72(13) pm
with the bromo ligand Br(1#) of a second molecule, thus
giving rise to a dimeric motif. Therefore, the effective coor-
dination around each Hg atom of the dimeric unit is better
described as distorted square pyramidal. The Hg···Hg# sep-
aration of 418.70(15) pm excludes any bonding interactions
between the two d10 centers. An intermolecular Hg···Br
contact of 342.7(3) pm exists also in the afore-mentioned
compound [(1,4,7,10,13,16-hexathiahiacyclooctadecane)-
Hg2Br4], which forms thus a 1D polymer considering the
effective coordination around Hg as trigonal bipyramidal
[17].
II
˚
1.62 vs. 1.373 A). Even compared to other Hg complexes
ligated by chelating thioether ligands, the bond distances of
3 are considerably elongated [13]. Thus, an averaged Hg-S
bond length of 261.2 pm has been encountered for the cat-
ionic compound [N(CH2CH2S-i-Pr)3HgCl]ϩ chelated by a
tripod-like tristhioether ligand [14], 269.3 pm have been re-
ported for the macrocyclic complex [bis(1,4,7-trithiacyclo-
decane)Hg]2 [15, 16]. Bond distances closer to those of 3
have been reported for the macrocyclic dinuclear complex
trabromo(1,4,7,10,13,16-hexathiahiacyclooctadecane)Hg2],
Synthesis of cis-[PtCl2{(PhSCH2)2SiC4H6}]
We synthesized furthermore the functionalized dithioether
ligand 1,1-bis(phenylthiomethyl)-2,5-dihydro-1H-silole (1b)
incorporating a five-membered silacyclopentene unit by re-
action of 1,1-dichlorosilacyclopenten-3-ene [18] with [(phe-
nylthio)methyl]lithium at Ϫ40 °C according Scheme 2. The
interest in this ligand system which was isolated as a waxy
solid, stems from the presence of a potentially reactive olef-
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Platinum and Mercury Complexes Chelated by (Phenylthiomethyl)silane Ligands
inic double bond. This functionalization may allow sub-
sequent transformations like hydrosilylation or polymeriz-
ation reactions. Compound 1b was then coordinated on
[PtCl2(PhCN)2] as chelating dithioether ligand forming the
complex cis-[PtCl2{(PhSCH2)2SiC4H6}] (4), which was iso-
lated in form of air-stable yellow crystals from chloroform.
This complex which is only moderately soluble in halogen-
ated solvents, is also fluxional according the 1H NMR spec-
tra recorded at variable temperature. At 298 K, the CH2SPh
protons give rise to a very broad hump at δ 2.64, which
sharpens on heating to give finally (323 K) a broadened sin-
Conclusion and Perspectives
We have shown that dithioether ligand (PhSCH2)2SiPh2
(1a) forms stable coordination compounds upon com-
plexation on platinum(II), however in the case of mer-
cury(II) the coordination is loose both in solution and the
crystalline state. We are currently investigating the possibil-
ity to alkylate or arylate the Pt-complex 2a by transmetall-
ation reaction with SnR4 [19, 20] in order to exploit the
reactivity of cis-[PtR(Cl){(PhSCH2)2SiPh2}] in organomet-
allic chemistry and catalysis. As an extension of this of work
we will also report in a forthcoming paper on the use of the
tetrakis-thioether (PhSCH2)4Si and (PhSCH2)4Ge [21, 22] as
tetradentate assembling ligands for the construction of
3
glet at δ 2.76 with a JPt,H coupling of 52 Hz.
homo-
and
heterodinuclear
systems
of
type
[LnM{(PhSCH2)2Si(CH2SPh)2}MLn] (M ϭ Cd, Hg, Cu,
Mn, Re, Pt).
Experimental Part
All reactions were performed in Schlenk-tube flasks under purified
nitrogen. Solvents were dried and distilled under nitrogen before
use, toluene and hexane over sodium, dichloromethane from P4O10.
Ϫ IR spectra have been recorded on a Nicolet Nexus 470 spec-
trometer, UV-vis spectra on a Uvikon-XLspectometer. Ϫ Elemental
C, H analyses were performed on a Leco Elemental Analyser CHN
1
900. Ϫ The H NMR spectra were recorded at 300.13 MHz on a
Scheme 2
Bruker Avance 300 instrument. 195Pt chemical shifts were measured
on a Bruker ACP 200 instrument (42.95 MHz) and externally refer-
enced to K2[PtCl4] in water with downfield chemical shifts reported
as positive. NMR spectra were recorded in pure CDCl3. Di-
phenylbis[(phenylthio)methyl]silane (1a) was prepared as pre-
viously described [23].
An X-ray diffraction study (Figure 7) shows that the co-
ordination around Pt is close to ideal square planar (rms
deviation from the plane defined by Pt-Cl(1)-Cl(2)-S(1)-S(2)
˚
0.053 A), the angles Cl(1)-Pt-Cl(2) and S(1)-Pt-S(2) being
88.69(4) and 92.07(4)°, respectively. The comparison with
2a (Table 1) reveals that the Pt-S distances are almost the
same, however the averaged Pt-Cl distances are slightly
shorter [231.72(13) vs. 229.79(12) pm]. Again, the phenyl
substituents of the sulphur atoms are in a cis-mode with
respect to the chelate ring, corresponding to a meso-confor-
mation.
Preparation of (PhSCH2)2SiC4H6 (1b)
A cooled solution of 0.24 mol of (phenylthiomethyl)lithium in
200 mL of diethyl ether/hexane, prepared from thioanisole and n-
BuLi in diethyl ether, was added at Ϫ40 °C to a solution of
0.08 mol of 1,1-dichlorosilacyclopent-3-ene in 30 mL of diethyl
ether. The reaction mixture was warmed to room temperature and
filtered. The solvent was evaporated in vacuo, and the residue was
purified by Kugelrohr distillation.Yield: 54 %. Anal. Calc. for
1
C18H20SiS2 (328.5): C, 65.80; H 6.14. Found: C, 66.3; H 6.3 %. H
3
NMR: δ ϭ 1.58 (m, 4H, SiCH2, JH, H ϭ 1.1 Hz), 2.49 (s, 4H,
3
SiCH2S), 5.95 (m, 2H, CϭCH, JH,H ϭ 1.1 Hz), 7.1Ϫ7.34 (m,
10 H, SC6H5).
Preparation of PtBr2{(PhSCH2)2SiPh2} (2b)
To a solution of 2a (347 mg, 0.5 mmol) in a 50:50 mixture of 12 ml
of dichloromethane/acetone was added an 10-fold excess of NaBr.
The suspension was then stirred for 24 h. The solvent then was
removed under reduced pressure and the residue extracted with
CH2Cl2. After concentration of the extract, layering with hexane
gave yellow crystals. (265 mg, 76 % yield). Anal. Calc. for
C26H24Br2PtS2Si (783.57): C, 39.85; H 3.09. Found: C, 39.77; H
3
Fig. 7 View of the molecular structure of
[PtCl2{(PhSCH2)2SiC4H6}] (4)
3.01 %. 1H NMR (328 K): δ ϭ 3.12 (s, 2H, JPt,H ϭ 56 Hz).
195Pt{1H} NMR (323 K): δ ϭ Ϫ2289 (s,br).
Z. Anorg. Allg. Chem. 2004, 630, 1955Ϫ1961
zaac.wiley-vch.de
 2004 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
1959

M. Knorr, H. N. Peindy, F. Guyon, H. Sachdev, C. Strohmann
ϭ 1.1 Hz), 7.44Ϫ7.86 (m, 10 H, SC6H5), UV-vis (CH2Cl2)
Preparation of PtI2{(PhSCH2)2SiPh2} (2c)
H
λmaxnm (ε, MϪ1cmϪ1) 230 (18000), 251 (16000).
This complex was obtained in a similar manner by adding NaI.
After concentration of the extract, layering with heptane gives or-
ange crystals of 2c Ⴇ 2 CH2Cl2, which loose the solvent molecules
during drying in vacuo. (355 mg, 81 % yield). Anal. Calc. for
C26H24I2PtS2Si (876.59): C, 35.59; H 2.76. Found: C, 35.17; H
Crystal structure determinations
A suitable crystal of each complex was mounted in a glass capillary
(3) or in an inert oil (perfluoropolyalkylether) (2a-c and 4) and
used for X-ray crystal structure determinations. Data of 3 were
collected on a Siemens AED2 diffractometer at 293(2) K. The
intensities were collected using Ω/2θ scans, and the intensities of
three standard reflections, which were measured after 90 min, re-
mained stable throughout each data collection. The intensities were
corrected for Lorentz and polarization effects. An empirical ab-
sorption correction based on the ψ-scans of three reflections was
employed. Data of 2a-c and 4 were collected on a Stoe IPDS dif-
fractometer at 173(2) K. The intensities were determined and cor-
rected by the program INTEGRATE in IPDS (Stoe & Cie, 1999).
An empirical absorption correction was employed using the
FACEIT-program in IPDS (Stoe & Cie, 1999)
3
2.64 %. 1H NMR: δ ϭ 2.99 (s, 2H, JPt,H ϭ 55 Hz), 7.28 Ϫ 7.83
(m, 20H, phenyl).
Preparation of HgBr2{(PhSCH2)2SiPh2} (3)
To a suspension of HgBr2 (360.5 mg, 1 mmol) in 10 ml of toluene
was added 1a (428 mg, 1 mmol). The solution was stirred at 25 °C
for 24 h. Layering the clear solution with hexane afforded colorless
crystals, suitable for X-ray diffraction. (594 mg, 75 % yield). Anal.
Calc. for C26H24Br2HgS2Si (789,08): C, 39.07; H 3.07. Found: C,
39.48; H 3.49 %.
Preparation of PtCl2{(PhSCH2)2SiC4H6} (4)
All structures were solved applying direct and Fourier methods,
using SHELXS-90 (G. M. Sheldrick, University of Göttingen 1990)
and SHELXL-97 (G. M. Sheldrick, SHELXL97, University of
Göttingen 1997). For each structure, the non-hydrogen atoms were
refined anisotropically. All of the H-atoms were placed in geometri-
cally calculated positions and each was assigned a fixed isotropic
displacement parameter based on a riding-model. Refinement of
the structures was carried out by full-matrix least-squares methods
To a solution of [PtCl2(PhCN)2] (471.8 mg, 1 mmol) in 8 ml of di-
chloromethane was added 1b (361 mg, 1.1 mmol). The solution was
stirred at 25 °C for 24 h. The solvent then was removed under re-
duced pressure and the residue rinsed with hexane. Recrystallis-
ation from dichloromethane/hexane gave yellow crystals, which
were filtered off and dried under vacuum. (619 mg, 89 % yield).
Anal. Calc. for C18H20Cl2PtS2Si (594.54): C, 36.36; H 3.39. Found:
C, 36.01; H 3.19 %. 1H NMR (323 K): δ ϭ 1.56 (s, 4H, SiCH2,
2
based on Fo using SHELXL-97. All calculations were performed
using the WinGX crystallographic software package, using the pro-
3JH, H ϭ 1.1 Hz), 2.76 (s, 4H, SiCH2S), 5.92 (s, 2H, CϭCH, JH,
3
Table 3 Crystallographic data for compounds 2a-c.
Identification code
2a
2b
2c
Empirical formula
Formula weight
Wavelength
Crystal system
Space group
C26H24Cl2PtS2Si
694.65
0.71073 A
C26H24Br2PtS2Si
783.57
0.71073 A
C26H24I2PtS2Si x 2 CH2Cl2
1047.40
0.71073 A
˚
˚
˚
orthorhombic
Pbca
a ϭ 10.159(2) A,
b ϭ 20.696(4) A,
c ϭ 23.695(5) A,
orthorhombic
Pbca
a ϭ 10.234(2) A,
b ϭ 20.867(4) A,
c ϭ 24.146(5) A,
triclinic
¯
P1
˚
˚
˚
˚
˚
˚
˚
˚
˚
Unit cell dimensions
a ϭ 13.238(3) A,
b ϭ 13.628(3) A,
c ϭ 14.383(3) A,
α ϭ 90
β ϭ 90°
γ ϭ 90°
α ϭ 90
β ϭ 90°
γ ϭ 90°
α ϭ 114.11(3)°
β ϭ 114.45(3)°
γ ϭ 92.82(3)°
3
3
3
˚
˚
˚
Volume
Z
Density (calculated)
Absorption coefficient
F(000)
4982.1(17) A
8
5156.5(18) A
8
1693.3(6) A
2
1.852 Mg/m3
6.077 mmϪ1
2704
2.019 Mg/m3
8.764 mmϪ1
2992
2.054 Mg/m3
6.459 mmϪ1
988
Crystal size mm
Theta range for data collection
Index ranges
0.20 x 0.20 x 0.10
2.39 to 25.0°
Ϫ12 Յ h Յ 12,
Ϫ24 Յ k Յ 24,
Ϫ28 Յ l Յ 28
40707
0.20 x 0.20 x 0.10
2.13 to 25.0°
Ϫ12 Յ h Յ 12,
Ϫ24 Յ k Յ 24,
Ϫ28 Յ l Յ 28
38348
0.30 x 0.20 x 0.20
2.25 to 27.0°
Ϫ15 Յ h Յ 15,
Ϫ15 Յ k Յ 16,
Ϫ15 Յ l Յ 17
12432
Reflections collected
Independent reflections
4380
4546
6863
[R(int) ϭ 0.1130]
Full-matrix least-squares on F2
4380 / 0 / 289
1.031
[R(int) ϭ 0.0755]
Full-matrix least-squares on F2
4549 / 0 / 274
1.052
[R(int) ϭ 0.0386]
Full-matrix least-squares on F2
6863 / 0 / 343
1.043
Refinement method
Data / restraints / parameters
Goodness-of-fit on F2
Final R indices [I>2sigma(I)]
R1 ϭ 0.0349,
wR2 ϭ 0.0841
R1 ϭ 0.0432,
wR2 ϭ 0.0868
R1 ϭ 0.0360,
wR2 ϭ 0.0822
R1 ϭ 0.0459,
wR2 ϭ 0.0852
R1 ϭ 0.0446,
wR2 ϭ 0.1133
R1 ϭ 0.0465,
wR2 ϭ 0.1147
R indices (all data)
Ϫ3
Ϫ3
Ϫ3
˚
˚
˚
Largest diff. peak and hole
1.037 and Ϫ1.841 e.A
0.937 and Ϫ1.988 e.A
4.340 and Ϫ4.319 e.A
1960
 2004 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
zaac.wiley-vch.de
Z. Anorg. Allg. Chem. 2004, 630, 1955Ϫ1961

Platinum and Mercury Complexes Chelated by (Phenylthiomethyl)silane Ligands
[2] N. Ruiz, A. Aaliti, J. Fornies-Camer, A. Ruiz, C. Claver, C.
Table 4 Crystallographic data for compounds 3 and 4.
J. Cardin, D. Fabbri, S. Gladiali, J. Organomet. Chem. 1997,
545Ϫ546, 79.
Identification code
3
4
[3] A. Gomis, G. Net, A. Ruiz, C. Claver, A. Alvarez-Larena,
Inorg. Chim. Acta 2001, 325, 58.
[4] A. Bastero, C. Claver, A. Ruiz, Catalysis Letters 2002, 82, 85.
[5] A. M. Masdeu-Bulto, M. Dieguez, E. Martin, M. Gomez,
Coord. Chem. Rev. 2003, 242, 159.
[6] P. Braunstein, T. Faure, M. Knorr, T. Stährfeld, A. DeCian,
J. Fischer, Gazz. Chim. Ital. 1995, 125, 35; M. Knorr,
C. Strohmann, P. Braunstein, Organometallics 1996, 15, 5653.
[7] M. Knorr, F. Guyon, I. Jourdain, S. Kneifel, J. Frenzel,
C. Strohmann, Inorg. Chim. Acta 2003, 350, 455.
[8] J.-R. Li, M. Du, R.-H. Zhang, X.-H. Bu, J. Mol. Struc. 2002,
607, 175.
Empirical formula
Formula weight
Wavelength
Crystal system
Space group
C26H24Br2HgS2Si
789.07
0.71073 A
C18H20Cl2PtS2Si
594.54
0.71073 A
˚
˚
monoclinic
P21/c
a ϭ 14.557(3) A,
b ϭ 20.108(4) A,
c ϭ 9.367(2) A,
monoclinic
P21/n
a ϭ 10.327(2) A,
b ϭ 12.623(4) A,
c ϭ 14.903(3) A,
˚
˚
˚
˚
˚
Unit cell dimensions
˚
α ϭ 90
α ϭ 90
β ϭ 97.33(3)°
γ ϭ 90°
β ϭ 91.19(3)°
γ ϭ 90°
3
3
˚
˚
Volume
Z
Density (calculated)
Absorption coefficient
F(000)
Crystal size (mm)
Theta range for data collection 2.41 to 25.0°
Index ranges
2728.1(10) A
4
1942.3(7) A
4
1.921 Mg/m3
8.781 mmϪ1
1504
2.033 Mg/m3
7.774 mmϪ1
144
[9] J. E. Huheey, E. Keiter, R. L. Keiter, Chimie Inorganique, De
´
Boeck Universite, ParisϪBruxell 1996, p. 546.
0.20 x 0.20 x 0.10
0.30 x 0.30 x 0.20
2.42 to 26.99°
Ϫ13 Յ h Յ 13,
Ϫ16 Յ k Յ 11,
Ϫ15 Յ l Յ 18
10024
[10] G. Marangoni, B. Pitteri, V. Bertolasi, P. Gilli, Inorg. Chim.
Acta 1995, 234, 173; B. Pitteri, G. Marangoni, L. Cattalini, L
Canovese, J. Chem. Soc. Dalton Trans. 1994, 169.
[11] P. Biscarini, L. Fusina, G. D. Nivellini, Inorg. Chem. 1971,
10, 2564.
Ϫ17 Յ h Յ 17,
0 Յ k Յ 23,
0 Յ l Յ 10
4517
Reflections collected
Independent reflections
4517
4136
[12] A. R. Sanger, Can. J. Chem. 1984, 62, 822.
[R(int) ϭ 0.0412]
Full-matrix
least-squares on F2
4136 / 0 / 217
1.025
Refinement method
Full-matrix
[13] An extreme long averagedHg-S bonding interaction of
317.2 pm of HgCl2 inside the cavity of an unsaturated 18-
membered thiacrown ether (hexagonal bipyramidal coordi-
nation) has been recently reported: T. Tsuchiya, T. Shimizu,
K. Hirabayashi, N. Kamigata, J. Org. Chem. 2003, 68, 3480.
[14] F. Cecconi, C. A. Ghilardi, S. Midollini, A. Orlandini, Inorg.
Chim. Acta 1998, 269, 274.
least-squares on F2
Data / restraints / parameters 4517 / 0 / 289
Goodness-of-fit on F2
1.063
Final R indices [I>2sigma(I)] R1 ϭ 0.0650,
wR2 ϭ 0.1593
R indices (all data)
R1 ϭ 0.0342,
wR2 ϭ 0.0899
R1 ϭ 0.0378,
wR2 ϭ 0.0932
R1 ϭ 0.0712,
wR2 ϭ 0.1658
2.657 and Ϫ1.875 e.A 1.544 and Ϫ2.860 e.A
Ϫ3
Ϫ3
˚ ˚
Largest diff. peak and hole
[15] M. L. Helm, C. M. Combs, D. G. VanDerveer, G. J. Grant,
Inorg. Chim. Acta 2002, 338, 182.
[16] for coordination of (1,4,8,11,15,18,22,25-octathiacyclooctaco-
sane) on HgBr2 see: A . J. Blake, W.-S. Li, V. Lippolis, A.
Taylor, M. Schröder, J. Chem. Soc., Dalton Trans. 1998, 2931.
[17] M. Herceg, D. Matkovic-Calogovic, Acta Cryst. 1992, C48,
1779.
grams SHELXS-90 and SHELXL-97. The crystallographic data for
each complex are given in Tables 3 and 4. The figures were drawn
using CrystalMaker for Mac 6.35.
Crystallographic data for the structural analysis have been de-
posited with the Cambridge Crystallographic Data Centre, CCDC
Nos CCDC 239987 Ϫ 239991 for compounds 2a-c, 3 and 4. Copies
of this information may be obtained free of charge from: The direc-
tor, CCDC, Union Road, Cambridge, CB2 IEZ, UK (Fax: ϩ44-
1223-336033; e-mail: deposit@ccdc.cam.ac.uk or www: http://
www.ccdc.cam.ac.uk)
[18] R. Damrauer, R. Simon, A. Lapoterie, G. Manuel, Y. T. Park,
W. P. Weber, J. Organomet. Chem. 1990, 391, 7.
[19] C. Eaborn, K. Kundu, A. Pidcock, J. Chem. Soc., Dalton
Trans. 1981, 933.
˚
[20] P. Kapoor, V. Kukuskin, K. Lövqvist, A. Oskarsson, Y. T.
Park, W. P. Weber, J. Organomet. Chem. 1996, 517, 71.
[21] C. Strohmann, S. Lüdtke, O. Ulbrich, Organometallics 2000,
19, 4223; C. Strohmann, D. Schildknecht, in: The Chemistry
of Organolithium Compounds, Z. Rappoport, I. Marek (eds.),
John Wiley Sons Ltd., Chichester 2004, p. 941.
[22] for recent work on the coodination ability of the related ligand
system (RSCH2)3SiMe see: W. C. Blackwell, D. Bunich, T. E.
Concolino, A. L. Rheingold, D. Rabinovich, Inorg. Chem.
Commun. 2000, 3, 325; H. W. Yim, K.-C Lam, A. L. Rheing-
old, D. Rabinovich, Polyhedron 2000, 19, 849; H. W. Yim, D.
Rabinovich K.-C Lam, J. A. Golen, A. L. Rheingold, Acta
Crystallogr. 2003, E59, m556.
Acknowledgements. We are grateful to the Deutschen Forschungsge-
meinschaft (DFG), the Fonds der Chemischen Industrie (FCI) and
`
the French Ministere de la Recherche et Technologie for financial
support. Furthermore we acknowledge Wacker-Chemie GmbH for
providing us with fine chemicals.
References
[1] E. W. Abel, S. K. Bhargava, K. G. Orrell, Progr. Inorg. Chem.
1984, 32, 1.
[23] C. Strohmann, S. Lüdtke, E. Wack, Chem. Ber. 1996, 129, 799.
Z. Anorg. Allg. Chem. 2004, 630, 1955Ϫ1961
zaac.wiley-vch.de
 2004 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
1961