Reactions of silicon-, germanium- and tin-containing carbene complexes of tungsten Ph3E-C≡W(OBut)3 (E=Si, Ge, Sn) with hydrogen chloride: Crystal structures of carbene complexes Ph3E-CH=WCl2 (OBut)2 (E=Si, Ge)

Article abstract of DOI:10.1016/j.jorganchem.2003.12.043

The novel organosilicon, -germanium and -tin-containing carbene complexes of tungsten of the type Ph₃E-CH= WCl₂(OBu^t)₂ (E=Si, Ge, Sn) have been prepared by the reaction of heteroelement-containing carbene complexes of tungsten Ph₃E-C≡W (OBu^t)₃ (E=Si, Ge, Sn) with hydrogen chloride. The tin-containing carbene complex was identified in solution by ¹H NMR spectroscopy. Silicon- and germanium-containing carbene complexes were isolated in high yields as crystalline solids and characterized by elemental analysis, IR, ¹H NMR, ¹³C NMR and ²⁹Si NMR spectroscopy and X-ray diffraction studies. The geometry of the W atoms in the compounds can be described as a distorted square pyramid.

Full text of DOI:10.1016/j.jorganchem.2003.12.043

Journal of Organometallic Chemistry 689 (2004) 1127–1130
www.elsevier.com/locate/jorganchem
Reactions of silicon-, germanium- and tin-containing
carbene complexes of tungsten Ph3E–CBW(OBut)3
(E ¼ Si, Ge, Sn) with hydrogen chloride: crystal structures
of carbene complexes Ph3E–CH@WCl2(OBut)2 (E ¼ Si, Ge)
*
A.V. Safronova, L.N. Bochkarev , N.E. Stolyarova, I.K. Grigorieva, I.P. Malysheva,
G.V. Basova, G.K. Fukin, Yu.A. Kurskii, S.Ya. Khorshev, G.A. Abakumov
G.A. Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences, Tropinina 49, Nizhny Novgorod 603950, Russian Federation
Received 2 September 2003; accepted 3 December 2003
Abstract
The novel organosilicon, -germanium and -tin-containing carbene complexes of tungsten of the type Ph3E–CH@WCl2(OBut)2
(E ¼ Si, Ge, Sn) have been prepared by the reaction of heteroelement-containing carbene complexes of tungsten Ph3E–CBW(OBut)3
1
(E ¼ Si, Ge, Sn) with hydrogen chloride. The tin-containing carbene complex was identified in solution by H NMR spectroscopy.
Silicon- and germanium-containing carbene complexes were isolated in high yields as crystalline solids and characterized by ele-
mental analysis, IR, 1H NMR, 13C NMR and 29Si NMR spectroscopy and X-ray diffraction studies. The geometry of the W atoms
in the compounds can be described as a distorted square pyramid.
Ó 2004 Elsevier B.V. All rights reserved.
Keywords: Carbene complexes; Tungsten; Silicon; Germanium; Tin; X-ray diffraction; Synthesis
1. Introduction
taining organosilicon, -germanium and -tin groups
bound to the carbene carbon atom.
Alkylidene complexes of tungsten are known to be
effective catalysts for the olefin metathesis reaction [1].
In the majority of such tungsten compounds, the car-
bene fragments contain alkyl groups; whereas there are
only a very few similar complexes with group 14 ele-
ment-containing organic substituents bonded to the
carbene carbon atom [2]. To the best of our knowledge,
systematic investigations aimed at finding effect of
composition and structure of the carbene fragments
upon the catalytic activity of these complexes in olefin
metathesis reactions have not been carried out.
2. Results and discussion
One of the known synthetic routes to carbene
complexes is the protonation of the metal–carbon
triple bond in carbene compounds of the type
R–CBW(OBut)3 (R ¼ But, CH2But) by hydrogen chlo-
ride [3]. Therefore, we used this reaction for the prepa-
ration of organosilicon, -germanium and -tin-containing
carbene complexes of tungsten from carbyne complexes
of the type Ph3E–CBW(OBut)3 (E ¼ Si, Ge, Sn) syn-
thesized by us recently [4].
Herein, we describe the synthesis and structural
characterization of tungsten carbene complexes con-
We found that the reaction of Ph3E–CBW(OBut)3
with two equivalents of HCl lead to the formation of
one equivalent of Ph3E–CH@WCl2(OBut)2 and one
equivalent of ButOH. So the reaction may be presented
by the following equation:
* Corresponding author. Tel.: +7-8312-66-8010; fax: +7-8312-66-
1497.
E-mail address: lnb@imoc.sinn.ru (L.N. Bochkarev).
0022-328X/$ - see front matter Ó 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2003.12.043

1128
A.V. Safronova et al. / Journal of Organometallic Chemistry 689 (2004) 1127–1130
Ph3E–CBWðOButÞ þ 2HCl
The geometry of the W(1) atoms in 1 and 2 can be de-
scribed as a distorted square pyramid. The deviations of
the W(1) atoms from the plane of the O(1)O(2)-
3
Toluene ðPentaneÞ
ButOH þ Ph E–CH@WCl2ðOButÞ
ƒƒƒƒƒƒƒƒƒ!
3
2
ꢀ78 °C
ꢀ
Cl(1)Cl(2) fragment are 0.48 A for 1 and 2. The C(9)–
E ¼ Si; Ge; Sn
W(1)–Cl and C(9)–W(1)–O angles vary in the range of
102.3(2)–103.7(1)° for 1 and 102.4(1)–104.5(1)° for 2.
The E(1)–C(9)–W(1) angles in 1 and 2 are similar
(136.1(3)° for 1 and 135.6(1)° for 2). Note that bond
angles E(1)–C(9)–H(9) for 1 and 2 (112.6(3.8)° and
113.6(1.4)°, respectively) and bond angles W(1)–C(9)–
H(9) for 1 and 2 (110.7(3.8)° and 110.8(1.4)°, respec-
tively) are practically equal.
The
tin-containing
carbene
complex
Ph3Sn–
CH@WCl2(OBut)2 was identified in solution by 1H
NMR. The compound appeared to be thermally unsta-
ble and decomposed at room temperature over the pe-
riod of 3 h. The silicon- and germanium-containing
carbene complexes were isolated as air-sensitive pale-
yellow crystalline solids. They were fully characterized
by elemental analysis, IR, 1H NMR, 13C NMR, 29Si
NMR spectroscopy and X-ray diffraction studies.
The Si(1)–C(Ph) distances in 1 are 1.854(4)–1.869(5)
A, which are shorter than Ge(1)–C(Ph) distances in 2
ꢀ
ꢀ
(1.943(2)–1.956(2) A). The difference between the E(1)–
C(Ph) distances in 1 and 2 is somewhat bigger than the
difference of the covalent radii of Si and Ge atoms
3. Crystal structures of Ph3E–CH@WCl2(OBut)2 (E = Si,
Ge)
ꢀ
(ꢁ0.06 A [5]). The same tendency is observed for the
ꢀ
ꢀ
Si(1)–C(9) (1.861(5) A) and the Ge(1)–C(9) (1.949(2) A)
distances. The W(1)–Cl and W(1)–O distances vary in
the narrow range of 2.373(1)–2.385(1) and 1.807(1)–
X-ray diffraction studies show that the complexes
Ph3E–CH@WCl2(OBut)2 (E ¼ Si (1), Ge (2)) contain
planar E(1)C(9)W(1)O(1)O(2) fragments (Fig. 1). The
deviations from planarity for the E(1)C(9)W(1)O(1)O(2)
ꢀ
1.830(3) A, respectively. The W(1)–C(9) distances also
ꢀ
ꢀ
are close to each other (1.868(5) A for 1 and 1.870(2) A
for 2). In the previously studied organosilicon-contain-
ing tungsten carbenes [6], the W@C(H)SiMe3 fragments
have the important structural parameters (W@C: 1.876
ꢀ
ꢀ
fragments are 0.018 A for 1 and 0.007 A for 2. The
geometry of the E(1) atom in both 1 and 2 is a distorted
tetrahedron. The C–E(1)–C angles vary in the range of
106.1(2)–112.0(2)° for 1 and 106.1(1)–112.9(1)° for 2.
ꢀ
ꢀ
and 1.872 A; Si–C: 1.852 and 1.832 A; WCSi: 136.4 and
138.5°) similar to those of complexes 1 and 2. Note that
the W(IV) complex [7] (but not W(VI) as in our case)
containing the analogous W@C(H)CMe3 fragment has
the neopentylidene ligand in a highly distorted geometry
where the W@C(H)–C angle is 168.7(3)° and the W@C–
H angle is 72.2(20)°.
4. Conclusion
E(1)
The novel organosilicon, -germanium and -tin-con-
taining carbene complexes of tungsten of the type Ph3E–
CH@WCl2(OBut)2 (E ¼ Si, Ge, Sn) have been prepared
by the reaction of heteroelement-containing carbene
complexes of tungsten with hydrogen chloride. The tin-
containing complex was identified in solution by 1H
NMR spectroscopy. The silicon- and germanium-con-
taining complexes were characterized by elemental
analysis, IR, 1H NMR, 13C NMR and 29Si NMR
spectroscopy and X-ray diffraction studies.
Fig. 1. The molecular structure of the complex 1 (E(1) ¼ Si) and 2
(E(1) ¼ Ge). The hydrogen atoms are omitted for clarity. Selected bond
ꢀ
lengths (A) and angles (°). 1: W(1)–O(1) 1.830(3), W(1)–O(2) 1.820(3),
W(1)–Cl(1) 2.374(1), W(1)–Cl(2) 2.373(1), W(1)–C(9) 1.868(5), Si(1)–
C(9) 1.861(5); O(1)W(1)Cl(1) 86.8(1), Cl(1)W(1)O(2) 87.7(1),
O(2)W(1)Cl(2) 87.2(1), O(1)W(1)Cl(2) 86.5(1), O(1)W(1)C(9) 103.1(2),
O(2)W(1)C(9) 102.3(2), Cl(1)W(1)C(9) 103.7(1), Cl(2)W(1)C(9)
103.6(1). 2: W(1)–O(1) 1.807(1), W(1)–O(2) 1.809(1), W(1)–Cl(1)
2.385(1), W(1)–Cl(2) 2.378(1), W(1)–C(9) 1.870(2), Ge(1)–C(9)
1.949(2); O(1)W(1)Cl(1) 87.0(1), Cl(1)W(1)O(2) 87.0(1), O(2)W(1)Cl(2)
86.7(1), O(1)W(1)Cl(2) 87.5(1), O(1)W(1)C(9) 102.4(1), O(2)W(1)C(9)
102.4(1), Cl(1)W(1)C(9) 103.4(1), Cl(2)W(1)C(9) 104.5(1).
5. Experimental
5.1. General
All manipulations were carried out in evacuated
sealed ampoules using standard Schlenk techniques.
The solvents were thoroughly dried and degassed.

A.V. Safronova et al. / Journal of Organometallic Chemistry 689 (2004) 1127–1130
1129
Table 1
Crystal data and structure refinement details for 1 and 2
Ph3Si–CH@WCl2(OBut)2 (1)
Ph3Ge–CH@WCl2(OBut)2 (2)
Empirical formula
Formula weight
Temperature (K)
Crystal system
C27H34Cl2O2SiW
673.38
C27H34Cl2O2GeW
717.88
110(2)
Monoclinic
183(2)
Monoclinic
Space group
Unit cell dimensions
C2=c
P21=c
a ¼ 34:791ð12Þ, b ¼ 8:881ð3Þ, c ¼ 19:671ð7Þ
a ¼ 16:9320ð13Þ, b ¼ 10:2807ð8Þ,
ꢀ
ꢀ
A; b ¼ 110:100(7)°
c ¼ 18:4200ð13Þ A; b ¼ 115:424(1)°
3
ꢀ
Volume (A )
5708(3)
8
1.567
2895.9(4)
4
1.647
Z
Density (calculated) (g/cm3)
Absorption coefficient (mmꢀ1
F ð000Þ
)
4.297
2672
5.212
1408
Crystal size (mm3)
0.1 ꢂ 0.2 ꢂ 0.8
0.45 ꢂ 0.35 ꢂ 0.25
2.23 to 29.01
h range for data collection (°)
Index ranges
Reflections collected
2.13 to 30.10
ꢀ48 6 h 6 48; ꢀ12 6 k 6 12; ꢀ27 6 l 6 27
33,327
ꢀ23 6 h 6 15; ꢀ13 6 k 6 13; ꢀ24 6 l 6 24
20,818
Independent reflections
Completeness to h ¼ 25:00° (%)
Absorption correction
Maximum/minimum transmission
Refinement method
8355 [Rint ¼ 0:0591]
99.3
7579 [Rint ¼ 0:0286]
98.4
SADABS
SADABS
0.3577/0.0675
0.3557/0.2026
Full-matrix least-squares on F2
8355/0/302
0.968
Full-matrix least-squares on F2
7579/16/417
1.038
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices [I > 2rðIÞ]
R indices (all data)
Largest difference peak and hole (eA )
R1 ¼ 0:0430, wR2 ¼ 0:1040
R1 ¼ 0:0697, wR2 ¼ 0:1178
3.787 and )1.597
R1 ¼ 0:0238, wR2 ¼ 0:0547
R1 ¼ 0:0300, wR2 ¼ 0:0568
0.948 and )1.506
3
ꢀ
Complexes Ph3SiCBW(OBut)3, Ph3GeCBW(OBut)3,
Ph3SnCBW(OBut)3 were prepared according to [4].
Infrared spectra were recorded with a ‘‘Perkin–Elmer-
577’’ spectrometer. The samples were prepared under
cmꢀ1): 1410, 1090, 730, 690, 490 (Ph3Si), 1140, 930 (W–
1
O–C), 1345, 1230 (But), 1005 (HC@). H NMR (200
1
MHz, toluene-d8) d 11.83 (s, 1H, HC@, JHaC ¼ 130:5,
2JhaW) ¼ 10.8), 7.66–7.71 (m, 6H, H(2)), 7.14–7.17 (m,
argon as Nujol mulls. H NMR, 13C NMR and 29Si
9H, H(3,4)), 1.45 (s, 9H, CH3), 1.07 (s, 9H, CH3). 13C
1
NMR spectra were obtained with a ‘‘Bruker DPX-200’’
spectrometer. The chemical shifts are reported in parts
per million with tetramethylsilane (0.00 ppm) as the
internal standard. GLC analysis was carried out using a
Tsvet-500 gas chromatograph with a 0.3 ꢂ 200 cm
stainless-steel column filled with SE-30 (5%) on Inerton
AW (with katharometer as a detector and helium as the
carrier gas).
NMR (50 MHz, toluene-d8)
d
264.19 (W@C,
1JC–183 ¼ 143:3), 137.44 (C(1)), 136.84 (CH(2)), 130.10
W
(CH(4)), 128.22 (CH(3)), 92.25 (WOCMe3), 91.20
(WOCMe3), 29.66 (CH3), 29.28 (CH3). 29Si NMR (39.7
MHz, toluene-d8) d )14.5 (Ph3Si, J
¼ 13:1).
2
29Si–183
W
5.3. Preparation of Ph3Ge–CH@WCl2(OBut)2 (2)
The procedure was essentially the same as described
above. From Ph3Ge–CBW(OBut)3 (0.88 g, 1.22 mmol)
and HCl gas (54.8 mL, 2.44 mmol) Ph3Ge–
CH@WCl2(OBut)2 was obtained as pale-yellow crystals
(0.82 g, 1.14 mmol, 93%). ButOH (76.97 mg, 1.04 mmol,
85%) was found in the volatile products by GLC analysis.
Complex 2 decomposed at 107–110 °C without melting.
Anal. Calc. for C27H34O2Cl2GeW: C, 45.17; H, 4.77.
Found: C, 45.58; H, 4.69. IR (KBr, cmꢀ1): 3030, 1460,
1080, 735, 690, 460 (Ph3Ge), 1150, 930 (W–O–C), 1350,
5.2. Preparation of Ph3Si–CH@WCl2(OBut)2 (1)
Two equivalents of gaseous HCl (33.2 mL, 1.48 mmol)
were condensed into a solution of Ph3SiCBW(OBut)3
(0.50 g, 0.74 mmol) in pentane or toluene (5 mL) at )78
°C. The solution turned orange-red immediately. Upon
warming to room temperature the solution became yel-
low-green. The solvent and volatile products were re-
moved in vacuo. ButOH (45.5 mg, 0.61 mmol, 83%) was
found in the volatile products by GLC analysis. The solid
product was recrystallized from pentane to give pale-
yellow crystals of Ph3Si–CH@WCl2(OBut)2 (0.44 g, 0.65
mmol, 88%). Complex 1 decomposed at 97–100 °C
without melting. Anal. Calc. for C27H34O2Cl2SiW: C,
48.16; H, 5.09. Found: C, 48.38; H, 5.10%. IR (KBr,
1
1230 (But), 1000 (HC@). H NMR (200 MHz, toluene-
1
d8) d 11.89 (s, 1H, HC@, JHaC ¼ 137:8; 2JHaW ¼ 7:2),
7.60–7.64 (m, 6H, H(2)), 7.14–7.19 (m, 9H, H(3,4)), 1.46
(s, 9H, CH3), 1.06 (s, 9H, CH3). 13C NMR (50 MHz,
1
toluene-d8) d 266.87 (W ¼ C, JC–183 ¼ 152:9), 137.94
W
(C(1)), 135.73 (CH(2)), 129.61 (CH(4)), 128.59 (CH(3)),

1130
A.V. Safronova et al. / Journal of Organometallic Chemistry 689 (2004) 1127–1130
2
91.75 (WOCMe3, JC–183 ¼ 8:7), 91.05 (WOCMe3,
W
CB2 1EZ, UK (Fax: +44-1223-336033; email: de-
posit@ccdc.cam.ac.uk).
2JC–183 ¼ 8:8), 29.66 (CH3), 29.26 (CH3).
W
5.4. Reaction of Ph3Sn–CBW(OBut)3 with HCl
Acknowledgements
This research was supported by the Grant of
President RF (Projects Nos. 5 58.2003.3 and No.
1652.2003.3) and the Russian Foundation for Basic
Research (Projects Nos. 02-03-32113 and 03-03-06118).
Gaseous HCl (5.80 mL, 0.26 mmol) was condensed to
a solution of Ph3Sn–CBW(OBut)3 (0.10 g, 0.13 mmol)
in toluene-d8 (1 mL) at )78 °C in NMR tube. 1H NMR
(200 MHz, toluene-d8)
d 12.04 (s, 1H, HC@,
1JHaC ¼ 142:0; 2JHaW ¼ 13:8).
References
5.5. Single crystal X-ray diffraction study of 1 and 2
[1] (a) M. Schuster, S. Blechert, Angew. Chem., Int. Ed. Engl. 36
(1997) 2037;
(b) R.H. Grubbs, S. Chang, Tetrahedron 54 (1998) 4413;
(c) R.R. Schrock, Tetrahedron 55 (1999) 8141.
[2] R.R. Schrock, Chem. Rev. 102 (2002) 145.
Single crystals of 1 and 2 for X-ray structure analysis
were obtained from pentane. The data were collected on
a SMART APEX diffractometer (graphite-monochro-
mated, Mo Ka-radiation, /–x-scan technique,
[3] J.H. Freudenberger, R.R. Schrock, Organometallics 4 (1985)
1937.
ꢀ
k ¼ 0:71073 A). The intensity data were integrated by
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Stolyarova, G.V. Basova, S.Ya. Khorshev, Yu.A. Kurskii, G.A.
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Kurskii, S.Ya. Khorshev, G.A. Abakumov, Russ. Chem. Bull.,
Int. Ed. 52 (2003), in press.
SAINT program [8]. The structures were solved by direct
methods and were refined on F2 using all reflections with
SHELXL-97 [9]. All non-hydrogen atoms were refined
anisotropically. The part of hydrogen atoms were placed
in calculated positions and refined in the ‘‘riding-model’’
and part of them were found from Fourier synthesis and
refined isotropically. SADABS [10] was used to perform
area-detector scaling and absorption corrections. The
details of crystallographic, collection and refinement
data are shown in Table 1.
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[8] Bruker, SAINTPlus Data Reduction and Correction Program v.
6.02a, Bruker AXS, Madison, WI, USA, 2000.
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[10] G.M. Sheldrick, SADABS v.2.01, Bruker/Siemens Area Detector
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USA, 1998.
6. Supplementary material
Crystallographic data have been deposited with the
Cambridge Crystallographic Data Centre, CCDC Nos.
214431 and 214432 for complexes 1 and 2, respectively.
Copies of these data may be obtained free of charge
from The Director, CCDC, 12 Union Road, Cambridge