Synthesis and structures of zeise-type complexes with vinylsilane ligands and quantum chemical analysis of the platinum-vinylsilane bonding

Article abstract of DOI:10.1002/zaac.200500110

Zeise-type complexes with vinylsilanes as π-ligands [K(18C6)][PtCl ₃(η²-CH₂=CHX)] (X = SiMe₃, 4; SiPh₃, 5; Si(OMe)₃, 6; 18C6 = 18-crown-6) and [K(18C6)]₂[(PtCl₃)₂

Full text of DOI:10.1002/zaac.200500110

Synthesis and Structures of Zeise-type Complexes with Vinylsilane Ligands and
Quantum Chemical Analysis of the Platinum؊Vinylsilane Bonding
Sebastian Schwieger, Christoph Wagner, Clemens Bruhn, Harry Schmidt, Dirk Steinborn*
Halle, Institut für Anorganische Chemie der Martin-Luther-Universität
Received March 4th, 2005.
Dedicated to Professor Herbert W. Roesky on the Occasion of his 70th Birthday
Abstract. Zeise-type complexes with vinylsilanes as π-ligands
[K(18C6)][PtCl3(η2-CH2ϭCHX)] (X
SiMe3, 4; SiPh3, 5;
Si(OMe)3, 6; 18C6 18-crown-6) and [K(18C6)]2[(PtCl3)2-
lengthenings and the pyramidalization angles of the olefins in the
vinylsilane complexes [PtCl3(η2-CH2ϭCHX)]Ϫ (X
SiMe3,
4c; SiPh3, 5c; Si(OMe)3, 6c) are the same as in Zeise’s anion
[PtCl3(η2-CH2ϭCH2)]Ϫ (8c) while the amount of the π back-dona-
tion in the vinylsilane complexes 4c؊6c is higher than that in the
ethylene complex 8c.
ϭ
ϭ
ϭ
{η2,η2-(CH2ϭCHSiMe2)2O}] (7) have been prepared by the reac-
tion of [K(18C6)]2[Pt2Cl6] (3) with the appropriate vinylsilanes. The
identities of the complexes have been confirmed by NMR spectro-
scopy as well as for 4, 5 and (PPh4)[PtCl3{η2-CH2ϭCHSi(OMe)3}]
(6Ј) also by single-crystal X-ray diffraction measurements. DFT
calculations exhibited, that the coordination induced CϭC bond
Keywords: Vinylsilane complexes; Platinum complexes; DFT-calcu-
lations; Olefin bonding
˚
1 Introduction
Zeise’s salt (0.04Ϫ0.06 A) as shown by the comparison of
the CϭC bond lengths in K[PtCl3(η2-CH2ϭCH2)]·H2O (2)
(neutron diffraction analysis; 1.375(4) A) [9] with that in
free ethylene (GED/IR: 1.336(3)Ϫ1.339(1) A [10]; X-ray
diffraction: 1.3124(3)Ϫ1.3142(3) A [11]). Although these
values must not be exaggerated due to uncertainties of the
measurements, this may point to a strong activation of
vinylsilanes by platinum(II). This receives further support
from the structures of [PtX2{Me2(CH2ϭCH)SiCH2ECH2Si-
(CHϭCH2)Me2-κ2C,CЈ,κE}] (X ϭ Br, E ϭ Te; X ϭ I, E ϭ
S) [12] having a coordinated and a non-coordinated vinyl-
silane group. In these complexes coordination induced
Reactions with stoichiometric and catalytic formation or
cleavage of siliciumϪelement bonds in the coordination
spheres of transition metals are of increasing interest to the
preparative organosilicium chemistry [1, 2]. Platinum com-
plexes may activate SiϪC bonds where, in general, the tend-
˚
˚
˚
2
3
ency of cleavage is in the order SiϪCsp > SiϪCsp > SiϪCsp
.
Thus, the SiϪCϵ bonds in alkynylsilanes are even suscep-
tible towards hydrolysis in alkaline solutions [3] and the for-
mation of platina-β-diketones [Pt2{(COR)2H}2(µ-Cl)2] from
reactions of hexachloroplatinic acid and alkynylsilanes pro-
ceeds with the cleavage of SiϪCϵ bonds [4]. Furthermore,
in wet acetone a slow decomposition of K[PtCl3(η2-CH2ϭ
CHSiMe3)] (1) yielding Zeise’s salt and hexamethyldisilox-
ane was observed. This cleavage of the ϭCHϪSi bond pro-
ved to be even catalytically [5]. Cleavage of SiϪC bonds in
vinyl- or alkynylsilanes by Zeise’s salt or Zeise’s dimer is
reported to proceed via the formation of Me3SiCl [3b, 6].
The single-crystal X-ray diffraction analysis of
[NBu4][PtCl3(η2-CH2ϭCHSiMe3)] (1Ј) exhibited a CϭC
˚
CϭC bond lengthenings of 0.08/0.13 A were found. These
two complexes and 1Ј are the only structurally charac-
terized platinum(II) complexes with η2-CH2ϭCHSiR3
ligands. On the other hand, molecular structures of
numerous platinum(II) complexes with (η2-CH2ϭCH)-
Me2SiOSiMe2(η2-CHϭCH2) ligands are known [13], show-
˚
ing a median of 1.415 A for the CϭC bond length (lower/
˚
upper quartile: 1.400/1.430 A; n ϭ 39, n ϭ number of ob-
servations) [14].
˚
bond length of 1.44(1) A [7]. Based on the determination of
These findings give the background for our interest in the
synthesis of Zeise-type complexes with vinylsilane ligands
and their structural characterization. For the synthesis we
used the reaction of [K(18C6)]2[Pt2Cl6] (3) [15] with vinyl-
silanes in methylene chloride. In an analogous way we suc-
ceeded to prepare not only an extended series of Zeise-type
olefin complexes [K(18C6)][PtCl3(η2-olefin)] [16] but also
alkyne complexes of the type [K(18C6)][PtCl3(η2-alkyne)]
[17]. To gain insight into the nature of the bonding of the
vinylsilane to the PtCl3Ϫ fragment quantum chemical calcu-
lations on the DFT level of theory were performed whereas
different vinylsilanes (Si(CHϭCH2)Me3, Si(CHϭCH2)Ph3,
Si(CHϭCH2)(OMe)3) have been considered.
the molecular structure of Si(CHϭCH2)Me3 by gas-phase
electron diffraction measurements (GED) (d(CϭC) ϭ
˚
1.36(1) A) [8], the coordination induced CϭC bond length-
˚
ening was found to be 0.08 A. This is much larger than the
coordination induced bond lengthening of ethylene in
* Prof. Dr. Dirk Steinborn
Institut für Anorganische Chemie
Martin-Luther-Universität Halle-Wittenberg
Kurt-Mothes-Straße 2
D-06120 Halle
E-mail: dirk.steinborn@chemie.uni-halle.de
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DOI: 10.1002/zaac.200500110
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Synthesis and Structures of Zeise-type Complexes with Vinylsilane Ligands
2 Results and Discussion
composition products. Analogously, a slow decomposition
of K[PtCl3(η2-CH2ϭCHSiMe3)] yielding Zeise’s salt was
observed [5]. Furthermore, cleavage of ϭCϪSi bonds in vi-
nylsilanes by catalytic amounts of PtII has been reported
[3b, 6b].
2.1 Syntheses
Reactions of the hexachlorodiplatinate [K(18C6)]2[Pt2Cl6]
(3) with excess of the vinylsilanes Si(CHϭCH2)Me3,
Si(CHϭCH2)Ph3, and Si(CHϭCH2)(OMe)3 in methylene
chloride at room temperature resulted with cleavage of the
PtϪClϪPt bridges in the formation of Zeise-type olefin
complexes 4؊6 (Scheme 1). The analogous reaction with
Me2(CH2ϭCH)SiϪOϪSi(CHϭCH2)Me2 proceeded with
the formation of the dinuclear platinum complex 7 where
the divinyldisiloxane acts as a bridging µ-bis(η2-olefin) li-
gand (Scheme 1). All these reactions take advantage of the
properties of the solvent (CH2Cl2) in which the crown ether
adduct of the potassium hexachlorodiplatinate (3) is partly
soluble. Furthermore, methylene chloride does not act as a
concurrent donor for the vinylsilanes due to its low donor
number (DN ϭ 1 [18]) and may promote the cleavage of
the PtϪClϪPt bridges due to its relatively high acceptor
number (AN ϭ 20.4 [18]). The complexes 4, 6, and 7 were
formed in moderate to good yields (35Ϫ90 %). The reaction
to form complex 5 (yield: 13 %) took more than two weeks
and was accompanied by the formation of greater amounts
of by-products. The identities of the complexes were con-
2.2 NMR Spectroscopic Characterization
For the vinylic protons of complexes 4؊7 spectra of higher-
order were observed; chemical shifts and coupling con-
stants given in Table 1 were obtained by spectrum simu-
lation as ABC and ABX spin systems, respectively. As an
example, in Figure 1 the experimental and simulated 1H
NMR spectra of 4 and 5 are shown. Whereas the 400 MHz
spectrum of the trimethylvinylsilane complex 4 (Figure 1a)
is clearly of higher order, the 500 MHz spectrum of the tri-
phenylvinylsilane complex (Figure 1b) is a borderline case.
In all cases the H,H-couplings between the vinyl protons
3
3
2
are in the expected range: Jtrans > Jcis >> Jgem
.
Compared with the non-coordinated vinylsilanes the
vinyl protons in the complexes 4؊7 are high-field shifted.
The coordination induced shifts (CIS; ∆δ ϭ δcoord.lig.
Ϫ
δnon-coord.lig.) are between Ϫ0.97 and Ϫ1.44 ppm. In all four
complexes the most high-field shifted proton has the lowest
CIS. In the mononuclear complexes 4؊6 the two olefinic
carbon atoms shift upfield on coordination by about
60 ppm. This is higher than the CIS in the analogous com-
plexes with non-functionalized olefins where the highfield
shifts are between 40 and 55 ppm [16]. The coordination
induced shifts in the dinuclear complex 7 (Ϫ46/Ϫ47 ppm)
are in that range. Furthermore, coordination gives rise to a
1
firmed by H and 13C NMR spectroscopy and for 4 and 5
also by single-crystal X-ray diffraction analyses. In the case
of the trimethylvinylsilane and trimethoxyvinylsilane com-
plexes (4 and 6) the usage of (PPh4)2[Pt2Cl6] (3Ј) instead of
3 resulted in the formation of the requisite tetraphenyl-
phosphonium complexes (PPh4)[PtCl3(η2-CH2ϭCHSiR3)]
(R ϭ Me, 4Ј; OMe, 6Ј). Complex 6Ј could be identified by
X-ray diffraction analysis.
3
decrease in the JH,H coupling constants by up to 5.3 Hz.
Scheme 1 Synthesis of Zeise-type complexes with vinylsilane ligands.
Complexes 4, 4Ј, and 5 showed partial decomposition in
solution (CDCl3, CH2Cl2) that may be due to traces of
water or HCl. The decomposition proceeded Ϫ at least in
part Ϫ with cleavage of the ϭCHϪSi bond and the forma-
tion of the anion of Zeise’s salt, [PtCl3(η2-CH2ϭCH2)]Ϫ as
This may be due to the lengthening of the CϪC double
bonds upon coordination and in the case of the trans coup-
lings also due to the decrease of the HϪCϪCϪH dihedral
angles as a consequence of the back-bending of the hydro-
gen atoms [19].
The molecular structure of 7 gives rise to expect three
stereoisomers as shown in Figure 2. The coordination of
one of the PtCl3 moieties on the re side of the olefin and
the other one on the si side results in the formation of the
meso form. The coordination twice on the same side (either
re/re or si/si) results in the formation of a pair of enantio-
mers (R,R and S,S, respectively) that are diastereomeric to
1
shown by means of H NMR spectroscopy and in an iso-
lated case also by X-ray diffraction analysis of the de-
composition product (PPh4)[PtCl3(η2-CH2ϭCH2)] (8). Al-
though the quality of the data set was limited (see Experi-
mental), the constitution of the complex could be deter-
mined unambiguously. In the case of the complex 4
Me3SiϪOϪSiMe3 and SiMe3Cl were identified as de-
Z. Anorg. Allg. Chem. 2005, 631, 2696Ϫ2704
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S. Schwieger, Ch. Wagner, C. Bruhn, H. Schmidt, D. Steinborn
Table 1 1H NMR spectroscopic data obtained by spectrum
simulation of higher-order multiplets of the vinylic protons in
complexes [K(18C6)][PtCl3(η2-CH2ϭCHSiR3)] (4؊6) and in
[K(18C6)]2[(PtCl3)2{η2,η2-(CH2ϭCHSiMe2)2O}] (7) (δ in ppm,
J in Hz).
4 (R ϭ Me)
5 (R ϭ Ph)
∆δ
6 (R ϭ OMe)
∆δ
7
∆
a)
δ
∆δ
δ
δ
∆δ
Figure 2 Two diastereomeric forms of complex 7 due to re/si coor-
dination (left, R,S isomer, meso form) and re/re coordination (right,
R,R isomer). Symmetry related methyl groups are denoted with the
same letter (aϪd).
H1 c)
H2
4.90
4.64
4.63
Ϫ1.24 5.52
Ϫ1.27 4.92
Ϫ1.02 4.88
Ϫ1.22 4.62
Ϫ1.44 4.68
Ϫ0.97 4.79
Ϫ1.14 4.88
Ϫ1.38 4.63
Ϫ1.12 4.62
Ϫ1.30
Ϫ1.33
Ϫ1.16
H3
b)
nJ
∆J
nJ
∆J
nJ
∆J
nJ
∆J
3JH,H,trans 15.63 Ϫ4.79 15.29 Ϫ4.97 15.39 Ϫ5.28 15.56 Ϫ5.01
3JH,H,cis
11.27 Ϫ3.38 11.18 Ϫ3.42 11.45 Ϫ3.67 11.38 Ϫ3.49
2JH,H,gem 3.13
Ϫ0.60 2.99 Ϫ0.49 3.14 Ϫ0.65 3.18 Ϫ0.62
2.3 Structures
The structures of the vinylsilane complexes 4, 5, and 6Ј are
shown in the Figures 3Ϫ5, selected structural parameters
are presented in Table 2. Crystals of complex 4 consist of
ion pairs ([K(18C6)]ϩ/[PtCl3(η2-CH2ϭCHSiMe3)]Ϫ) with
specific cation-anion interactions. The Kϩ ion has close
contacts to the trans and to one of the cis chloro ligands
of the trichloro(olefin)platinate anion (K···Cl1 3.290(2) A,
K···Cl2 3.185(2) A). These distances are only slightly longer
than those in the solid KCl (3.146 A). There are no unusual
a) ∆δ ϭ δ(coordinated ligand) Ϫ δ(non-coordinated ligand)
n
n
b) ∆J ϭ J(coordinated ligand) Ϫ J(non-coordinated ligand)
c) Numbering scheme:
˚
˚
˚
contacts between these ion pairs. The shortest distance
˚
the meso form. Thus, as shown in the Figure 2, the silicium-
bound methyl groups are no longer chemically equivalent.
In accordance with this, in the 13C NMR spectrum four
methyl carbon resonances were found. The shift difference
a/b and c/d, respectively, is 1.0 ppm, whereas that between
the two diastereomers (a/c and b/d, respectively) is very
small (0.02 ppm). The signal intensity makes clear, that the
complex formation is not diastereoselective. In the 1H
NMR spectrum three signals for the methyl groups were
found: One broader signal at 0.49 ppm and two signals for
the high-field shifted protons (0.32 ppm) with a shift differ-
ence of only 0.003 ppm.
between non-hydrogen atoms is 3.446(7) A (O6···C3Ј).
Crystals of the triphenylvinylsilane complex 5 are built up
analogously. The K···Cl contacts within the ion pair are
3.149(2) A (K···Cl2) and 3.320 (2) A (K···Cl1). The first one
is even as long as those in the solid KCl (3.146 A). There are
no unusual contacts between these ion pairs. The shortest
˚
˚
˚
˚
distance between non-hydrogen atoms is 3.28(1) A
(O6···C12Ј). Analogous ion pair formation via short K···Cl
contacts has also been found in other olefin and alkyne
complexes of the type [K(18C6)][PtCl3(η2-olefin/alkyne)].
In the complex (PPh4)[PtCl3{η2-CH2ϭCHSi(OMe)3}] (6Ј)
no specific cation-anion interactions were found. Thus,
1
Figure 1 Experimental (bottom) and simulated (top) H NMR spectrum of the vinyl region of a) complex 4 (R ϭ Me; 400 MHz) and
b) complex 5 (R ϭ Ph; 500 MHz). # platinum satellites, * impurity.
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Synthesis and Structures of Zeise-type Complexes with Vinylsilane Ligands
Figure 3 Structure of [K(18C6)][PtCl3(η2-CH2ϭCHSiMe3)] (4).
Displacement ellipsoids are drawn at 30 % probability; H atoms
were omitted for clarity.
Figure 5 Structure of the anion [PtCl3{η2-CH2ϭCHSi(OMe)3}]Ϫ
in crystals of 6Ј. Displacement ellipsoids are drawn at 30 % proba-
bility.
˚
Table 2 Selected interatomic distances (in A) and angles (in °) in
complexes [K(18C6)][PtCl3(η2-CH2ϭCHSiR3)] (4, 5) and in
(PPh4)[PtCl3{η2-CH2ϭCHSi(OMe)3}] (6Ј).
4 (R ϭ Me)
5 (R ϭ Ph)
6Ј (R ϭ OMe)
PtϪCl1
PtϪCl2
PtϪCl3
PtϪC1
PtϪC2
C1ϪC2
SiϪC1
SiϪC3
SiϪC4
SiϪC5
SiϪC1ϪC2
Cl2ϪPtϪCl3
Cl1ϪPtϪCl2
Cl1ϪPtϪCl3
K···Cl1
2.322(1)
2.316(1)
2.320(1)
2.161(5)
2.149(5)
1.398(8)
1.884(5)
1.874(5)
1.873(5)
1.876(5)
127.0(4)
177.57(6)
89.68(5)
89.59(5)
3.290(2)
3.185(2)
Ϫ155.9(3)
85.7(3)
2.331(2)
2.293(2)
2.300(2)
2.154(7)
2.134(6)
1.402(8)
1.861(6)
1.867(6)
1.889(7)
1.879(5)
132.7(5)
178.95(6)
89.06(7)
90.89(7)
3.320(2)
3.149(2)
Ϫ164.8(3)
79.8(4)
2.311(2)
2.302(1)
2.306(1)
2.137(5)
2.141(6)
1.402(8)
1.862(5)
1.611(4)a)
1.640(5)b)
1.629(4)c)
130.2(4)
177.91(5)
89.75(5)
90.88(5)
Ϫ
Figure 4 Structure of [K(18C6)][PtCl3(η2-CH2ϭCHSiPh3)] (5).
Displacement ellipsoids are drawn at 30 % probability; H atoms
were omitted for clarity.
K···Cl2
Ϫ
PtϪC1ϪSiϪC4
151.2(3)d)
81.6(4)
the shortest contact between non-hydrogen atoms of the
Pt,Cl1,Cl2,Cl3/Pt,C1,C2e)
˚
anion to a tetraphenylphosphonium cation is 3.385(8) A
a) SiϪO1. b) SiϪO2. c) SiϪO3. d) PtϪC1ϪSiϪO2. e) Angle between least-
(O1···C15Ј). The distance to another cation is only slightly
longer (Cl3···C7Ј 3.428(5) A).
square planes.
˚
The coordination geometry of the anions [PtCl3(η2-
CH2ϭCHSiR3]Ϫ is as expected. The platinum atoms are
square-planar coordinated by three chloro ligands and an
olefin ligand that lies nearly perpendicular to the PtCl3
plane (interplanar angles 79.8(4)Ϫ85.7(3)°). The CϭC
ordination induced back-bending of the substituents at the
CϭC carbon atoms in the complexes 4, 5, and 6Ј cannot be
derived from the measurements: On the one side, the pre-
cision of the positions of the vinylic H atoms is too low.
On the other side, quantum chemical calculations (see 2.4)
indicate that the back-bending of the silyl substituents is
also caused by steric effects; thus, it cannot be regarded to
be a measure for the back-donation.
˚
bonds are slightly longer (1.398(8)Ϫ1.402(8) A) than that
˚
in Zeise’s salt (1.375(4) A [9]). To evaluate the coordination
induced bond lengthening, these values have to be com-
pared with the CϭC bond lengths in non-coordinated
vinylsilanes. These cover a broad range (structural unit
˚
CH2ϭCHSiC3: median: 1.313 A; lower/upper quartile
2.4 Quantum Chemical Calculations
˚
1.277/1.329 A; n ϭ 26) and only few data are available for
˚
simple vinylsilanes (Si(CHϭCH2)4: 1.316(2)Ϫ1.320(2) A,
In order to gain deeper insight into the nature of the side-
on bonding of the vinylsilanes to platinum quantum chemi-
cal calculations on the DFT level of theory have been per-
formed. To find out an appropriate hybrid functional and
˚
[20]; Si(CHϭCH2)Me3: 1.36(1) A [8]). Overall, on the basis
of these data it is difficult to derive coordination induced
bond lengthenings in these complexes. Furthermore, the co-
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S. Schwieger, Ch. Wagner, C. Bruhn, H. Schmidt, D. Steinborn
basis sets, various calculations of the anion of Zeise’s salt,
[PtCl3(η2-C2H4)]Ϫ (8c), and of Si(CHϭCH2)4 have been
performed. Comparison with the reported crystal structures
of Zeise’s salt [9] and tetravinylsilane [20] revealed, that the
hybrid functional MPW1PW91 [21], a triple-ζ valence basis
set for Pt with a polarization function added (TZVP) as
provided by Ahlrichs and co-workers [22] and split-valence
basis sets with a polarization function added for the other
atoms (6-31G*) give a good fit between calculated and ex-
perimental values (see 3.4). The structures of the anions
[PtCl3(η2-CH2ϭCHSiR3)]Ϫ (R ϭ Me, 4c; Ph, 5c, OMe, 6c)
along with the structure of Zeise’s anion 8c for comparison
are shown in the Figure 6. Selected geometric parameters
are given in Table 3.
Table 3 Calculated structural parameters of vinylsilane platinate
complexes [PtCl3(η2-CH2ϭCHSiR3)]Ϫ (4c؊6c) and of Zeise’s an-
ion [PtCl3(η2-CH2ϭCH2)]Ϫ (8c) for comparison (interatomic di-
stances in A, angles in °). In parentheses the requisite values of the
non-coordinated olefins (calculated on the same level of theory)
are given.
˚
8c
4c
5c
6c
(R ϭ Me) (R ϭ Ph) (R ϭ OMe)
C1ϪC2
SiϪC1
1.402 1.408
(1.328) (1.336)
1.410
(1.336)
1.888
(1.876)
2.160
2.131
2.340
2.349
2.354
178.23
84.54
23.65
(0.47)
17.56
(0.30)
19
1.408
(1.337)
1.865
(1.852)
2.155
2.132
2.345
2.355
2.348
178.27
85.44
23.09
(0.22)
17.69
(0.06)
14
Ϫ
1.889
(1.878)
PtϪC1
PtϪC2
PtϪCl1
PtϪCl2
2.133 2.168
2.133 2.136
2.348 2.345
2.355 2.359
2.355 2.353
177.81 177.70
90.00 83.93
16.97d) 20.12
(0.00) (0.00)
17.10 17.12
(0.00) (0.00)
In general, the calculated and experimentally found
structures are in a good agreement. The slightly shorter
PtϪCl bonds trans to the olefin ligands over those cis to
PtϪCl3
Cl2ϪPtϪCl3a)
Pt,Cl1,Cl2,Cl3/Pt,C1,C2b)
C1,H1,Si/C1ϪC2c)
˚
the olefin ligands (∆ 0.003Ϫ0.014 A) can be rationalized in
terms of the trans influence olefin > ClϪ [23] and antibond-
ing Pt(dπ)ϪCl(pπ) interactions [24]. Whereas the ethylene li-
gand in 8c was found to be perpendicular to the complex
plane (exp.: 89.0°; calcd. from data given in [9]), in the
vinylsilane complexes 4c؊6c the interplanar angles between
the complex plane PtCl3 and the PtC2 plane are between
83.9 and 85.4° (exp.: 79.8(4)Ϫ85.7(3)°).
C2,H2,H3/C1ϪC2c)
Є(PtϪC1ϪSi) Ϫ Є(PtϪC1ϪH1) 0e)
Є(PtϪC2ϪH3) Ϫ Є(PtϪC2ϪH2) 0
15
1
2
1
a) All angles CltransϪPtϪClcis are between 89.82 and 91.09°. b) Angles
between least-square planes. c) Pyramidalization angle α: angle between the
least-square plane (CH2 and CHSi, respectively) and the C1ϪC2 axis.
d) C1,H1,H4/C1ϪC2. e) Є(PtϪC1ϪH4) Ϫ Є(PtϪC1ϪH1).
Figure 6 Calculated equilibrium structures of [PtCl3(η2-CH2ϭCHX)]Ϫ: a) X ϭ SiMe3, 4c; b) X ϭ SiPh3, 5c; c) X ϭ Si(OMe)3, 6c;
d) X ϭ H, 8c.
2700
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zaac.wiley-vch.de
Z. Anorg. Allg. Chem. 2005, 631, 2696Ϫ2704

Synthesis and Structures of Zeise-type Complexes with Vinylsilane Ligands
As generally found in complexes having substituted olefin
Table 4 Bond characteristics of vinylsilanes in Zeise-type comple-
xes [PtCl3(η2-CH2ϭCHX)]Ϫ (X ϭ SiMe3, 4c; SiPh3, 5c; Si(OMe)3,
6c) and in the parent complex 8c (X ϭ H) for comparison (De ϭ
bond dissociation energy, ∆Eint ϭ instantaneous interaction energy,
ligands [25], the PtϪC1 bonds are longer than the PtϪC2
˚
bonds (∆ 0.023Ϫ0.032 A). The coordination induced
lengthening of the CϭC bonds in the vinylsilane complexes
4c؊6c and in the ethylene complex 8c are the same
∆Eprep ϭ preparation energy, all energies in kcal/mol; Pπ/Pπ*
ϭ
population of the π/π* orbitals of the olefin ligands obtained by
NBO analysis, values in electrons).
˚
(0.071Ϫ0.074 A). Furthermore, for the back-bending of the
olefin substituents, measured by the pyramidalization angle
α (C2,H2,H3/C1ϪC2, see Table 3), were also found only
minor differences (17.1Ϫ17.7°). On the other hand, the pyr-
amidalization angles C1,H1,Si/C1ϪC2 are slightly larger
(20.1Ϫ23.7°). But these angles cannot be regarded as a pro-
per measure for the back-donation because the SiR3 groups
are more strongly back-bended than the hydrogen atoms
H1 (Є(PtϪC1ϪSi) Ϫ Є(PtϪC1ϪH1) ϭ 14Ϫ19°; for com-
parison: Є(PtϪC2ϪH2) Ϫ Є(PtϪC2ϪH3) ϭ 1Ϫ2°, see
Table 3). This could account for a larger back-donation
from platinum to C1 (compared with C2) or to a steric
hindrance between the bulky SiR3 groups and the PtCl3
moiety.
8c
(X ϭ H)
4c
5c
6c
(X ϭ SiMe3) (X ϭ SiPh3) (X ϭ Si(OMe)3)
a)
De
De
37.6
34.8
Ϫ48.7
33.3
31.2
Ϫ48.2
14.9
25.9
24.2
Ϫ47.7
21.8
32.2
30.2
Ϫ51.2
19.0
a) b)
a)
∆Eint
∆Eprep
11.1
Charge decomposition
donation (d)
back-donation (b)
repulsive
polarization
residual term
d/b
0.369
0.295
Ϫ0.626
0.347
0.350
Ϫ0.691
0.356
0.368
Ϫ0.717
0.373
0.352
Ϫ0.706
Ϫ0.013
1.25
Ϫ0.018
0.99
Ϫ0.021
0.97
Ϫ0.027
1.06
NBO analysis
Pπ (NBO)c)
1.629 (2.000) 1.636 (1.972) 1.640 (1.967)
0.347 (0.000) 0.354 (0.013) 0.365 (0.012)
1.622 (1.967)
0.356 (0.010)
The bond dissociation energies De of the olefin ligands
in the complexes 4c؊6c and 8c
Pπ* (NBO)c)
a) BSSE corrected. b) ZPE corrected. c) Values of the noncoordinated olefins
are given in parentheses.
[PtCl3(η2-CH2ϭCHX)]Ϫ Ǟ [PtCl3]Ϫ ϩ CH2ϭCHX
tioning that recently Kim et al. [31] have shown that in
metalϪolefin complexes the electron population in π*-anti-
bonding orbitals (Pπ*) of olefin ligands is more correctly
used to evaluate the degree of back-bonding than the coor-
dination induced bond lengthening, because the latter one
is caused by the degree of π-back-bonding and the degree
of σ-bonding.
The NBO analyses of the noncoordinated olefins (calcu-
lated on the same level of theory) show for the vinylsilanes
a reduced population of the π-orbitals (Pπ: 1.967Ϫ1.972)
were found to be 34.8 (8c, X ϭ H) > 31.2 (4c, X ϭ SiMe3)
> 30.2 (6c, X ϭ Si(OMe)3) > 24.2 (5c, SiPh3) (values in
kcal/mol; BSSE and ZPE corrected). The value calculated
for 8c is in good agreement with other calculations [24, 26].
The partitioning of the bond dissociation energy De into a
preparation term (∆Eprep) and an instantaneous interaction
term (∆Eint) (see Ref. [27] for an explanation of the funda-
mental steps) shows, that the lowering of De from 8c to 5c
is mainly caused by increasing preparation energies in the
same sequence (Table 4). This can be rationalized in terms
of the increasing bulkiness of the substituents H < SiMe3
< Si(OMe)3 < SiPh3.
and
a
partial population of the π*-orbital (Pπ*:
0.010Ϫ0.013) (Table 4). This indicates hyperconjugative in-
teractions between the π system and SiϪC/SiϪO bonds. In
the complexes 4c؊6c one of the substituents on Si is nearly
antiperiplanar to the PtϪC1 bonds (PtϪC1ϪSiϪC4
Ϫ154.3/Ϫ151.8° 4c/5c; PtϪC1ϪSiϪO2 155.0°, 6c; see Fig-
ure 6). These SiϪC/SiϪO bonds are significantly longer
The mode of bonding of the vinylsilane ligands was
examined by means of the charge decomposition analysis
(CDA) of Frenking [28]. As it is clear for Zeise’s salt, the
low residual terms (Table 4) give evidence that also the ana-
logous vinylsilane complexes 4c؊6c can be discussed in
terms of the DewarϪChattϪDuncanson model [29]. The
ratio d/b between the donation (d) and back-donation (b)
proved to be in the vinylsilane complexes significantly
smaller than in Zeise’s anion (0.97Ϫ1.06 versus 1.25). The
reason is clearly the higher Pt Ǟ vinylsilane back-donations
in 4c؊6c compared with Pt Ǟ ethylene back-donation in
8c. This is also confirmed by the electron populations of
the π*-orbitals of the olefins (Pπ*) obtained by NBO analy-
sis [30], although the difference in the back-donation be-
tween the vinylsilane complexes 4c؊6c on the one side and
the ethylene complex 8c on the other side is smaller in this
analysis. The higher degree of the π back-donation in 4c؊6c
is neither reflected in CϭC bond lengthening (∆d:
˚
(0.013Ϫ0.027 A) than the other ones, indicating hypercon-
jugative interactions. This may also exert influence on the
Pt Ǟ vinylsilane back-donation.
3 Experimental
3.1 General
All reactions were performed under Ar atmosphere using standard
Schlenk techniques. Solvents were dried (Et2O and thf over Na-
benzophenone, CHCl3, CDCl3 and CH2Cl2 over CaH2) and dis-
tilled prior to use. 1H and 13C NMR spectra were recorded on
Varian Gemini 200, VXR 400, and Unity Inova 500 NMR spec-
trometers. Chemical shifts are relative to CHCl3 (δ ϭ 7.24) and
CDCl3 (δ ϭ 77.0) as internal references and Si(CH3)4 in CDCl3
(δ ϭ 0) as external reference. If necessary, assignments of NMR
signals were revealed by running spectra in APT mode. The NMR
spectroscopic investigations of complexes 4؊7 were performed in
˚
˚
0.071Ϫ0.074 A in 4c؊6c versus 0.074 A in 8c) nor in the
pyramidalization of the olefins (α: 17.1Ϫ17.7° in 4c؊6c
versus 17.0/17.1° in 8c) upon coordination. It is worth men-
Z. Anorg. Allg. Chem. 2005, 631, 2696Ϫ2704
zaac.wiley-vch.de
 2005 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
2701

S. Schwieger, Ch. Wagner, C. Bruhn, H. Schmidt, D. Steinborn
melted NMR tubes. IR spectra were recorded on a Galaxy FT-IR
spectrometer Mattson 5030 using CsBr pellets. Microanalyses were
performed by the University of Halle microanalysis laboratory
using CHNS-932 (LECO) and Vario EL (elementar Analysensys-
teme) elemental analysers. The complex [K(18C6)]2[Pt2Cl6] (3) was
synthesized according to a published method [15], (PPh4)2[Pt2Cl6]
(3Ј) was prepared as reported in [32]. All other chemicals were com-
mercially available.
added. The brown precipitate was filtered off and discarded. Then
the filtrate was concentrated to 3 ml and treated with diethyl ether
(3 ml) resulting in a brown precipitate that was filtered off and
discarded again. This procedure was repeated two times until a
yellow precipitate (5) could be isolated. This was washed with di-
ethyl ether (2 ϫ 2 ml) and dried briefly in vacuo.
Yield: 70 mg (13 %); m.p. 75 °C (dec.).
IR (CsBr): ν 3067 (w), 2898 (m), 1472 (w), 1428 (m), 1351 (m), 1284 (w),
1249 (m), 1111 (s), 963 (m), 837 (w), 702 (m), 511 (m), 490 (w) cmϪ1 1H
.
NMR (500 MHz, CDCl3): δ ϭ 3.54 (s, 24H, 18C6), 4.86Ϫ4.94 (m, 2H,
SiCHϭCH2), 5.49Ϫ5.54 (m, 1H, SiCHϭCH2), 7.27Ϫ7.82 (m, C6H5). 13C
NMR (125 MHz, CDCl3): δ ϭ 69.8 (s, 18C6), 72.7/73.6 (s/s, SiCHϭCH2/
SiCHϭCH2), 127.5/129.0/135.3/136.8 (s/s/s/s, C6H5). 29Si NMR (100 MHz,
CDCl3): δ ϭ Ϫ16.2 (s).
3.2 Syntheses
3.2.1 Preparation of [K(18C6)][PtCl3(η2-CH2ϭ
CHSiMe3)] (4)
Further signals indicate the presence of non-reacted Si(CHϭ
CH2)Ph3 (ca. 27 %) and an impurity of [K(18C6)][PtCl3(η2-CH2ϭ
CH2)] (8Ј) (ca. 3 %):
To a suspension of [K(18C6)]2[Pt2Cl6] (3) (121 mg, 0.1 mmol) in
CH2Cl2 (3 ml) Si(CHϭCH2)Me3 (112 mg, 1.1 mmol) was added via
a syringe and the reaction mixture was stirred overnight. The vol-
ume of the resulting yellow solution was reduced in vacuo to 1 ml,
the precipitate was filtered off, and diethyl ether (5 ml) was added
slowly to the clear filtrate. The crystals formed were filtered,
washed with diethyl ether (2 ϫ 1 ml), and dried briefly in vacuo.
Yield: 63 mg (45 %); m.p. 80Ϫ84 °C (dec.). Anal. Calc. for
C17H36Cl3KO6PtSi (705.08): C, 28.96; H, 5.15; Cl, 15.08. Found:
C, 29.29; H, 5.14; Cl, 14.55 %.
2
1H NMR (500 MHz, CDCl3): δ ϭ 4.46 (sϩd, JPt,C ϭ 63.25 Hz, 8Ј), 6.67
(dd, 3JH,H, trans ϭ 20.17 Hz, 3JH,H, cis ϭ 14.67 Hz, 1H, Ph3SiCHϭCH2), 7.78
3
2
(dd, JH,H, trans ϭ 20.17 Hz, JH,H ϭ 3.67 Hz, 1H, Ph3SiCHϭCHH, cis to
3
2
SiPh3), 6.29 (dd, JH,H, cis ϭ 14.67 Hz, JH,H ϭ 3.67 Hz, 1H, Ph3SiϪCHϭ
CHH, trans to SiPh3). 13C NMR (125 MHz, CDCl3): δ ϭ 67.8 (s, 8Ј), 127.9/
129.6/136.0 (s/s/s, C6H5Si), 29Si NMR (100 MHz, CDCl3): δ ϭ Ϫ17.3 (s,
Ph3SiCHϭCH2).
IR (CsBr): ν 1472 (w), 1455 (w), 332 (w) cmϪ1. 1H NMR (400 MHz, CDCl3):
3.2.3 Preparation of [K(18C6)][PtCl3{η2-CH2ϭ
CHSi(OMe)3}] (6)
δ ϭ 0.26 (sϩd, 2JSi,H ϭ 6.64 Hz, 9H, (CH3)3Si), 3.66 (s, 24H, 18C6), 4.5Ϫ4.8
2
2
(mϩd, br, JPt,H ϭ 64 Hz, 2H, CH2ϭCHSi), 4.8Ϫ5.0 (mϩd, br, JPt,H
ϭ
64 Hz, 1H, CH2ϭCHSi). 13C NMR (100 MHz, CDCl3, APT mode): δ ϭ 0.7
(s, (CH3)3Si), 70.1 (s, 18C6), 73.5 (s, CH2ϭCHSi), 81.4 (s, CH2ϭCHSi).
To [K(18C6)]2[Pt2Cl6] (3) (220 mg, 0.18 mmol) in CH2Cl2 (6 ml)
Si(CHϭCH2)(OMe)3 (590 mg, 4.0 mmol) was added and stirred
overnight. Then the solution was concentrated in vacuo to 3 ml.
The brown precipitate was filtered off and to the yellow filtrate
diethyl ether (3 ml) was added dropwise. The resulting pink precipi-
tate was filtered off, the clear pale yellow filtrate was concentrated
in vacuo to 1 ml. The product was obtained by adding diethyl ether
(10 ml) to the solution. The filtered product was washed with di-
ethyl ether (3 ϫ 2 ml) and dried briefly in vacuo.
Yield: 95 mg (35 %); m.p. 90Ϫ92 °C (dec.). Anal. Calc. for
C17H36Cl3KO9PtSi (753.08): C, 27.11; H, 4.82; Cl, 14.12. Found:
C, 26.41; H, 4.95; Cl, 13.27 %.
IR (CsBr): ν 2096 (m), 1473 (w), 1351 (s), 1107 (s), 963 (s) cmϪ1 1H NMR
.
(200 MHz, CDCl3): δ ϭ 3.63 (s, 24H, 18C6), 3.69 (s, 9H, OCH3), 3.98Ϫ4.85
(m, 3H, CH2ϭCHSi). 13C NMR (100 MHz, CDCl3): δ ϭ 51.1 (s, OCH3),
68.1 (s, CH2ϭCHSi), 70.1 (s, 18C6), 74.4 (s, CH2ϭCHSi).
Repetition of NMR measurements after 3 d revealed partial
decomposition. Product composition (from 1H NMR spectrum):
[K(18C6)][PtCl3(η2-CH2ϭCHSiMe3)] (4): [K(18C6)][PtCl3(η2-CH2ϭ
CH2)] (8Ј) : SiMe3Cl (9) : (Me3Si)2O (10) ഠ 33 % : 22 % : 27 %
: 16 %.
1H NMR (200 MHz, CDCl3): δ ϭ 0.04 (s, 10), 0.27 (s, Si(CH3)3, 4), 0.41 (s,
9), 3.67 (s, 18C6), 4.46 (sϩd, 2JPt,H ϭ 64.74 Hz, CH2ϭCH2, 8Ј), 4.6Ϫ5.1 (m,
SiCHϭCH2, 4). 13C NMR (125 MHz, CDCl3): δ ϭ Ϫ2.3 (s), Ϫ1.7 (s), Ϫ0.5
1
1
(s), 0.5 (sϩd, JSi,C ϭ 53.2 Hz, (CH3)3Si, 4), 1.9 (s, 10), 3.2 (sϩd, JSi,C
ϭ
2
57.6 Hz, 9), 64.1 (s), 68.1 (sϩd, JPt,C ϭ 191.9 Hz, CH2ϭCH2, 8Ј), 70.1 (s,
1
1
18C6), 73.4 (sϩd, JPt,C ϭ 189.5 Hz, CH2ϭCHSi, 4), 81.4 (sϩd, JPt,C
ϭ
185.2 Hz, CH2ϭCHSi, 4), 86.5 (s). 29Si NMR (99 MHz, CDCl3): δ ϭ Ϫ0.4
(s, 4), 7.3 (s, 10), 31.2 (s, 9).
An analogous procedure, using (PPh4)2[Pt2Cl6] (3Ј) instead of 3,
resulted in the formation of (PPh4)[PtCl3(η2-CH2ϭCHSiMe3)] (4Ј).
2
1H NMR (400 MHz, CDCl3): δ ϭ 0.07 (sϩd, JSi,H ϭ 6.64 Hz, 9H, SiCH3),
In a similar procedure, (PPh4)2[Pt2Cl6] (3Ј) was used instead of 3.
From the mother liquor of this experiment well-shaped crystals of
(PPh4)[PtCl3{η2-CH2ϭCHSi(OMe3)}] (6Ј) suitable for single-crys-
tal X-ray measurement could be obtained.
4.25Ϫ4.52 (mϩd, br, 2JPt,H ϭ 62.7 Hz, 2H, CH2ϭCHSi), 4.54Ϫ4.81 (m, 1H,
CH2ϭCHSi), 7.48Ϫ7.54 (m, 8H, o-CH), 7.66Ϫ7.71 (m, 8H, m-CH),
7.76Ϫ7.81 (m, 4H, p-CH). 13C NMR (100 MHz, CD2Cl2): δ ϭ 0.7 (s, CH3Si),
1
73.2 (s, CH2ϭCHSi), 80.4 (s, CH2ϭCHSi), 117.9 (d, JP,C ϭ 89.8 Hz, i-C),
3
2
131.0 (d, JP,C ϭ 12.9 Hz, m-C), 134.8 (d, JP,C ϭ 10.3 Hz, o-C), 136.1 (d,
4JP,C ϭ 3.0 Hz, p-C). 29Si NMR (100 MHz, CDCl3): δ ϭ Ϫ0.8 (s).
3.2.4 Preparation of [K(18C6)]2[(PtCl3)2{η2,η2-
(CH2ϭCHSiMe2)2O}] (7)
From the mother liquor of this experiment, well-shaped crystals
of (PPh4)[PtCl3(η2-CH2ϭCH2)] (8) suitable for single-crystal X-ray
measurement were obtained.
A mixture of [K(18C6)]2[Pt2Cl6] (3) (100 mg, 0.08 mmol) and
O[Si(CHϭCH2)Me2]2 (380 mg, 2,0 mmol) in CH2Cl2 (3 ml) was
stirred overnight at room temperature. Then the clear solution was
concentrated in vacuo to 1 ml and the precipitate filtered off. To
the clear yellow filtrate diethyl ether (10 ml) was added dropwise,
the precipitate was filtered, washed with diethyl ether (2 ϫ 2 ml)
and dried briefly in vacuo.
3.2.2 Preparation of [K(18C6)][PtCl3(η2-CH2ϭ
CHSiPh3)] (5)
A mixture of [K(18C6)]2[Pt2Cl6] (3) (365 mg, 0.30 mmol) and
Si(CHϭCH2)Ph3 (1.0 g, 3.5 mmol) in CH2Cl2 (10 ml) was stirred
at room temperature for 17 days. The resulting dark red solution
was concentrated in vacuo to 3 ml and diethyl ether (3 ml) was
Yield: 100 mg (90 %); m.p. 99 °C (dec.).
IR (CsBr): ν 2898 (m), 2826 (w), 1626 (w), 1473 (w), 1453 (w), 1351 (m),
1250 (m), 1109 (s) 963 (m), 838 (m), 800 (m) cmϪ1 1H NMR (400 MHz,
.
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zaac.wiley-vch.de
Z. Anorg. Allg. Chem. 2005, 631, 2696Ϫ2704

Synthesis and Structures of Zeise-type Complexes with Vinylsilane Ligands
˚
˚
CDCl3): δ ϭ 0.323 (s, 3H, SiCH3), 0.326 (s, 3H, SiCH3), 0.49 (s, 6H, SiCH3),
Mr ϭ 668.86, monoclinic, P21/a, a ϭ 25.448(4) A, b ϭ 7.1759(7) A,
3.63 (s, 48H, 18C6), 4.60Ϫ4.65 (m, 4H, CH2ϭCHSi), 4.85Ϫ4.92 (m, 2H,
CH2ϭCHSi). 13C NMR (100 MHz, CDCl3, APT mode): δ ϭ 2.48 (s, SiCH3),
2.50 (s, SiCH3), 3.48 (s, SiCH3), 3.50 (s, SiCH3), 70.1 (s, 18C6), 73.1 (s, CH2ϭ
CHSi), 80.1 (s, CH2ϭCHSi). 29Si NMR (99 MHz, CDCl3): δ ϭ 0.1 (s).
3
˚
˚
c ϭ 13.265(2) A, β ϭ 91.29(2)°, V ϭ 2421.7(6) A , Z ϭ 4,
µ(Mo Kα) ϭ 6.204 mmϪ1, F(000) ϭ 1296, θ range 2.19Ϫ25.00°,
refln. coll. 9933, data/restraints/parameter 4027/1/280, R1 ϭ 0.0543
(I > 2σ(I)), wR2 ϭ 0.1651 (all data).
3.3 X-ray structure determinations
3.4 Computational details
Crystals suitable for X-ray diffraction analyses were grown from
mother liquors at room temperature by slow addition of diethyl
ether to a solution of the complexes in dichloromethane (4, 6Ј) and
by addition of pentane to a solution of 5 in acetone, respectively.
Intensity data were collected on a STOE IPDS (4, 6Ј) and a STOE
STADI IV (5) diffractometer, respectively, using graphite mono-
All DFT calculations were performed by employing the Gaus-
sian98 program package [34]. With various hybrid functionals and
basis sets the structures of the anion of Zeise’s salt (8c) and tetra-
vinylsilane were optimized [35]. Comparison with the experimen-
tally found structures K[PtCl3(η2-C2H4)]·H2O (neutron diffraction
analysis) [9] and Si(CHϭCH2)4 (single-crystal X-ray diffraction
measurement) [20] revealed that the functional BHandHLYP as im-
plemented in Gaussian98 proved to be the best to describe the
structural parameters of tetravinylsilane, whereas the functional
LSDA [36] performed well in describing the bond lengths in Zeise’s
anion. A functional satisfyingly describing both, the free vinylsilane
ligand as well as the organometallic compound, was found to be
Barone and Adamo’s Becke-style one parameter functional using
modified Perdew-Wang exchange and Perdew-Wang 91 correlation
(MPW1PW91) [21]. A triple-ζ valence basis set was used for Pt
with a polarization function added (TZVP) as provided by Ahlrichs
and co-workers [22]; for its core orbitals an effective core potential
with consideration of relativistic effects has been used [37]. For all
atoms split-valence basis sets with a polarization function added
were used (6-31G*). More extensive basis sets have been tested with
little effect on the quality of the structure. Only TZVPP basis sets
on all atoms gave significantly better results but with respect to the
size of the molecules to be calculated this is inappropriate due to
limited computer resources. All systems have been fully optimized
without any symmetry restrictions. The resulting geometries were
characterized as equilibrium structures by the analysis of the force
constants of normal vibrations [35]. Electron populations were ob-
tained by the natural bond orbital (NBO) analysis as implemented
in Gaussian98 [38]. The charge decomposition analyses (CDA)
were performed with the program CDA2.1 by Dapprich and Frenk-
ing [39].
˚
chromatized Mo-Kα radiation (λ ϭ 0.71073 A) at 220(2) K (4, 6Ј)
and 213(2) K (5), respectively. A summary of the crystallographic
data, the data collection parameters and the refinement parameters
is given in Table 5. Absorption correction for 5 was applied using
ψ-scans (Tmin/Tmax ϭ 0.12/0.32) and numerically for 4 (Tmin/Tmax ϭ
0.32/0.72) and 6Ј (Tmin/Tmax ϭ 0.33/0.62). The structures were
solved by direct methods with SHELXS-97 [33] and refined using
full-matrix least-squares routines against F2 with SHELXL-97 [33].
Non-hydrogen atoms were refined with anisotropic displacement
parameters and hydrogen atoms with isotropic displacement par-
ameters. The positions of hydrogen atoms in 4 and 6Ј were found
in the difference Fourier map except for the H atoms of the Me3Si
group and on C15 in 4 that were added to the model in calculated
positions according to the riding model. In 5 all positions of H
atoms were calculated (riding model) except those of the vinylic
group (H1a/H1b, H2) that were found in the difference Fourier
map. H1a/H1b were freely refined sharing the same distance and
isotropic displacement parameters. Crystallographic data (exclud-
ing structure factors) for these structures have been deposited at
the Cambridge Crystallographic Data Center (CCDC) as Sup-
plementary Publication Nos. CCDC-281856 (4), CCDC-281857
(5), and CCDC-281858 (6Ј). Copies of the data can be obtained
free of charge on application to the CCDC, 12 Union Road, Cam-
bridge, CB2 1EZ, U.K. (fax. (internat.) ϩ44-1223-336033;
e-mail: deposit@ccdc.cam.ac.uk). Crystallographic data for
(PPh4)[PtCl3(η2-CH2ϭCH2)] (8): Empirical formula C26H24Cl3PPt,
Table 5 Crystallographic and data collection parameters for 4, 5, and 6Ј.
4
5
6Ј
Empirical formula
Mr
C17H36Cl3KO6PtSi
705.09
monoclinic
P21/c
C32H42Cl3KO6PtSi
891.29
monoclinic
P21/n
13.538(1)
15.732(1)
18.280(3)
109.20(2)
3676.7(8)
4
C29H32Cl3O3PPtSi
789.05
monoclinic
P21/c
12.908(2)
7.449(1)
32.311(6)
95.54(2)
3092.2(9)
4
1.695
4.916
1552
Crystal system
Space group
˚
a /A
7.633(2)
˚
b /A
22.294(4)
16.268(3)
100.99(2)
2717.4(9)
4
1.723
5.683
˚
c /A
β /°
3
˚
V /A
Z
Dcalc /g cmϪ1
µ(Mo Kα) /mmϪ1
F(000)
1.610
4.219
1776
1392
Θ range /°
2.23Ϫ26.04
21152
4356
5267 (0.0764)
5267 / 0 / 366
1.049
0.0312, 0.0736
0.0413, 0.0774
1.012 and Ϫ1.407
1.64Ϫ24.99
5776
4318
4725 (0.0244)
4725 / 1 / 407
1.018
0.0283, 0.0737
0.0332, 0.0801
0.541 and Ϫ1.155
1.93Ϫ25.06
16351
4513
5350 (0.0508)
5350 / 0 / 451
1.079
0.0301, 0.0756
0.0385, 0.0804
0.839 and Ϫ0.923
Refln. collected
Refln. obs. [I > 2σ(I)]
Refln. independent (Rint
)
Data/restraints/parameters
Goodness-of-fit on F2
R1, wR2[I > 2σ(I)]
R1, wR2 (all data)
Largest difference peak and hole /e A
Ϫ3
˚
Z. Anorg. Allg. Chem. 2005, 631, 2696Ϫ2704
zaac.wiley-vch.de
 2005 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
2703

S. Schwieger, Ch. Wagner, C. Bruhn, H. Schmidt, D. Steinborn
Acknowledgements. The authors gratefully acknowledge financial
support by the Deutsche Forschungsgemeinschaft and Merck
KGaA (Darmstadt) for gifts of chemicals.
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Z. Anorg. Allg. Chem. 2005, 631, 2696Ϫ2704