Synthesis and structures of silicon-, germanium-, and tin-containing tungsten carbyne complexes (ButO)3W≡C-EPh 3 and [(ButO)3W≡C]2EPh 2 (E = Si, Ge, Sn)

Article abstract of DOI:10.1023/B:RUCB.0000011869.83994.94

New tungsten carbyne complexes (Bu^tO)₃W≡C- SiPh₃, [(Bu^tO)₃W≡C]₂SiPh ₂, [(Bu^tO)₃W≡C]₂GePh ₂, and [(Bu^tO)₃W≡C]

Full text of DOI:10.1023/B:RUCB.0000011869.83994.94

2140
Russian Chemical Bulletin, International Edition, Vol. 52, No. 10, pp. 2140—2145, October, 2003
Synthesis and structures of siliconꢀ, germaniumꢀ, and tinꢀcontaining
tungsten carbyne complexes
(ButO)3W≡C—EPh3 and [(ButO)3W≡C]2EPh2 (E = Si, Ge, Sn)
A. V. Safronova, L. N. Bochkarev,ꢀ N. E. Stolyarova, I. K. Grigor´eva, I. P. Malysheva,
G. V. Basova, G. K. Fukin, Yu. A. Kurskii, S. Ya. Khorshev, and G. A. Abakumov
G. A. Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences,
49 ul. Tropinina, Nizhny Novgorod 603950, Russian Federation.
Fax: +7 (831 2) 66 1497. Eꢀmail:lnb@imoc.sinn.ru
New tungsten carbyne complexes (ButO)3W≡C—SiPh3, [(ButO)3W≡C]2SiPh2,
[(ButO)3W≡C]2GePh2, and [(ButO)3W≡C]2SnPh2 were prepared by the reactions of (ButO)6W2
with Ph3SiC≡C—Pr or Ph2E(C≡C—Pr)2 (E = Si, Ge, Sn) in individual crystalline form in
48—80% yields. The structures of both the (ButO)3W≡C—GePh3 and (ButO)3W≡C—SnPh3
compounds synthesized earlier and the new complexes were established by Xꢀray diffraction
analysis.
Key words: carbyne complexes, synthesis, Xꢀray diffraction analysis.
It is known1—3 that the tungsten carbyne complexes
under analogous conditions to form the previously unꢀ
known trinuclear siliconꢀ, germaniumꢀ, and tinꢀcontainꢀ
ing tungsten carbyne complexes [(ButO)3W≡C]2EPh2
(E = Si (5), Ge (6), Sn (7)).
(ButO)3W≡C—R (R = Me, Et, Pr, But, Ph) serve as cataꢀ
lysts for metathesis of acetylenic hydrocarbons. Data
on analogous tungsten complexes containing organoꢀ
silicon, ꢀgermanium, or ꢀtin substituents at the carbyne
carbon atom and their catalytic properties are scarce.3
Earlier,4 we have reported that the reactions of
elementꢀsubstituted acetylenes Ph3GeC≡C—Pr and
Ph3SnC≡C—Et with tungsten alkoxide (ButO)6W2
afforded the germaniumꢀ and tinꢀcontaining
carbyne complexes (ButO)3W≡C—GePh3 (1) and
(ButO)3W≡C—SnPh3 (2), respectively. In the
present study, we used this procedure for the prepaꢀ
ration of a new siliconꢀcontaining tungsten complex
(ButO)3W≡C—SiPh3 (3).
E = Si (5), Ge (6), Sn (7)
i. 20 °C, 10—30 min, pentane.
After separation of compound 4 by vacuum sublimaꢀ
tion, complexes 5, 6, and 7 were isolated in individual
form in 48, 74, and 70% yields, respectively, as airꢀunꢀ
stable colorless crystals readily soluble in organic solvents.
The structures of compounds 1 and 2, which we have
synthesized earlier, as well as of complexes 5—7 prepared
in the present study were established by Xꢀray diffraction
analysis.
Xꢀray diffraction study of the crystalline
carbyne complexes (ButO)3W≡C—GePh3 (1) and
(ButO)3W≡C—SnPh3 (2) demonstrated that they are
isostructural (Fig. 1). The W and Ge (Sn) atoms in comꢀ
pounds 1 and 2 have a distorted tetrahedral coordination
(Table 1). The W(1)—C(13) distances in complex 1
(1.785(7) and 1.757(6) Å*) are close to the analogous
i. 20 °C, 1 h, pentane.
According to the 1H NMR spectroscopic data, the
reaction afforded new complex 3 and known compound 4
in virtually 100% yields. After separation of compound 4
by vacuum sublimation, complex 3 was obtained in the
crystalline state in 80% yield as airꢀunstable colorless crysꢀ
tals readily soluble in organic solvents.
We found that diphenyldi(pentꢀ1ꢀynꢀ1ꢀyl)silane, ꢀgerꢀ
mane, and ꢀstannane Ph2E(C≡CPr)2 (E = Si, Ge, Sn)
also readily reacted with ditungsten hexaꢀtertꢀbutoxide
* Hereinafter, the second values of the geometric characteristics
for complexes 1 and 2 correspond to another independent
molecule.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2028—2032, October, 2003.
1066ꢀ5285/03/5210ꢀ2140 $25.00 © 2003 Plenum Publishing Corporation

Syntheses of tungsten carbyne complexes
C(23)
Russ.Chem.Bull., Int.Ed., Vol. 52, No. 10, October, 2003
2141
C(22)
C(21)
C(8)
C(6)
C(5)
C(24)
C(25)
C(7)
C(20)
O(2)
C(4)
C(31)
C(30)
C(13)
E(1)
C(2)
O(1)
C(29)
W(1)
C(1)
C(26)
C(27)
C(11)
C(3)
C(28)
O(3)
C(14)
C(10)
C(19)
C(9)
C(12)
C(18)
C(15)
C(16)
C(17)
Fig. 1. Molecular structures of complexes 1 and 2: Е(1) = Ge(1) (1), Sn(1) (2).
distances in complex 2 (1.757(7) and 1.749(6) Å). The
Ge(1)—C(13) distances in complex 1 are 1.898(7) and
1.927(6) Å. The Sn(1)—C(13) distances in complex 2 are
2.110(7) and 2.116(6) Å. The Ge—C(Ph) and Sn—C(Ph)
distances in complexes 1 and 2 are in the ranges of
1.939(7)—1.971(7) and 2.130(6)—2.151(6) Å, respecꢀ
Table 1. Selected bond lengths (d) and bond angles (ω) in complexes 1 and 2*
Bond
d/Å
Angle
ω/deg
Angle
ω/deg
Complex 1
Complex 1
Complex 2
W(1)—C(13)
W(1)—O(1)
W(1)—O(2)
W(1)—O(3)
Ge(1)—C(13)
Ge(1)—C(14)
Ge(1)—C(20)
Ge(1)—C(26)
1.785(7)/1.757(6)
1.867(5)/1.854(5)
1.871(5)/1.863(5)
1.860(5)/1.870(5)
1.898(7)/1.927(6)
1.959(7)/1.946(8)
1.967(8)/1.971(7)
1.939(7)/1.952(7)
C(13)—W(1)—O(3)
C(13)—W(1)—O(1)
O(3)—W(1)—O(1)
C(13)—W(1)—O(2)
O(3)—W(1)—O(2)
O(1)—W(1)—O(2)
C(13)—Ge(1)—C(26) 110.5(3)/111.8(3)
C(13)—Ge(1)—C(14) 111.3(3)/111.9(3)
C(26)—Ge(1)—C(14) 108.7(3)/108.3(3)
C(13)—Ge(1)—C(20) 107.0(3)/108.7(3)
C(26)—Ge(1)—C(20) 111.7(3)/110.1(3)
C(14)—Ge(1)—C(20) 107.5(3)/105.9(3)
W(1)—C(13)—Ge(1) 176.7(4)/179.2(4)
110.0(3)/108.3(3)
106.1(3)/108.4(3)
111.6(2)/110.4(2)
107.8(3)/108.6(3)
111.2(2)/111.5(2)
109.9(2)/109.4(2)
C(13)—W(1)—O(3)
C(13)—W(1)—O(1)
O(1)—W(1)—O(3)
C(13)—W(1)—O(2)
O(2)—W(1)—O(3)
O(2)—W(1)—O(1)
C(13)—Sn(1)—C(26)
C(13)—Sn(1)—C(14)
C(14)—Sn(1)—C(26)
C(13)—Sn(1)—C(20)
C(26)—Sn(1)—C(20)
C(14)—Sn(1)—C(20)
W(1)—C(13)—Sn(1)
108.5(3)/108.0(3)
107.9(3)/107.5(3)
111.5(2)/111.1(2)
107.2(2)/108.2(2)
110.2(2)/111.4(2)
111.4(2)/110.5(2)
107.2(2)/111.6(2)
111.6(2)/112.7(3)
110.5(2)/108.2(2)
115.4(2)/107.3(2)
105.4(2)/110.3(2)
106.7(3)/106.6(3)
171.9(4)/172.2(4)
Complex 2
W(1)—C(13)
W(1)—O(1)
W(1)—O(2)
W(1)—O(3)
Sn(1)—C(13)
Sn(1)—C(14)
Sn(1)—C(20)
Sn(1)—C(26)
1.757(7)/1.749(6)
1.869(4)/1.860(4)
1.867(5)/1.863(4)
1.870(4)/1.870(5)
2.110(7)/2.116(6)
2.140(6)/2.130(6)
2.150(6)/2.139(6)
2.145(6)/2.151(6)
* The geometric characteristics of another independent molecule are given after a slash.

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Safronova et al.
C(22)
C(31)
C(30)
C(13)
C(20)
C(12)
O(3)
C(21)
O(5)
C(32)
C(19)
C(29)
C(10)
C(9)
C(11)
C(27)
C(28)
C(14)
O(2)
W(1)
W(2)
C(18)
O(4)
C(6)
C(1)
C(7)
O(1)
O(6)
E(1)
C(24)
C(15)
C(8)
C(5)
C(16)
C(26)
C(23)
C(33)
C(2)
C(17)
C(34)
C(25)
C(4)
C(3)
C(38)
C(35)
C(37)
C(36)
Fig. 2. Molecular structure of complex 7 (Е(1) = Sn(1)). The Е(1) atoms in complexes 5 (Е(1) = Si(1)) and 6 (Е(1) = Ge(1)), unlike
that in complex 7, lie on a twofold axis.
tively, and are somewhat longer than the Ge(1)—C(13)
and Sn(1)—C(13) distances. The difference in the Ge—C
and Sn—C bond lengths in complexes 1 and 2 correꢀ
sponds, in fact, to the difference between the covalent
radii of the Sn (1.36 Å 5) and Ge (1.19 Å 5) atoms.
than the Si(Ge, Sn)≡C distances. The differences in the
Si—C, Ge—C, and Sn—C bond lengths in complexes 5—7
correspond to the differences between the covalent radii
Table 2. Selected bond lengths (d) and bond angles (ω) in comꢀ
plexes 5 and 6
The W(1)—C(13)—Ge(1) and W(1)—C(13)—Sn(1)
angles are correspondingly 176.7(4)° and 179.2(4)° in
complex 1 and 171.9(4)° and 172.2 (4)° in complex 2.
Xꢀray diffraction study of the crystalline dicarbyne
complexes [(ButO)3W≡C]2EPh2 (E = Si (5), Ge (6),
Sn (7)) also demonstrated that these compounds are strucꢀ
turally similar (Fig. 2). The W and Si (Ge, Sn) atoms in
compounds 5—7, like those in complexes 1 and 2, have a
distorted tetrahedral coordination (Tables 2 and 3).
The W(1)—C(1) distances are 1.777(3), 1.761(2),
and 1.759(3) (1.762(3)) Å*, respectively, for comꢀ
plexes 5—7. The Si(1)—C(1), Ge(1)—C(1), and
Sn(1)—C(1) distances in 5—7 are 1.842(3), 1.923(2), and
2.107(3) (2.111(3)) Å, respectively. The Si—C(Ph),
Ge—C(Ph), and Sn—C(Ph) distances are 1.885(3),
1.957(2), and 2.140(3) (2.140(3)) Å, respectively, which,
like those in complexes 1 and 2, are somewhat longer
Parameter
Complex 5
Complex 6
Bond
W(1)—C(1)
W(1)—O(1)
W(1)—O(2)
W(1)—O(3)
E(1)—C(1)
E(1)—C(14)
Angle
C(1)—W(1)—O(1)
C(1)—W(1)—O(2)
C(1)—W(1)—O(3)
O(1)—W(1)—O(2)
O(1)—W(1)—O(3)
O(3)—W(1)—O(2)
C(1)—E(1)—C(1A)
C(1)—E(1)—C(14)
C(1)—E(1)—C(14A)
C(14)—E(1)—C(14A)
W(1)—C(1)—E(1)
d/Å
1.777(3)
1.859(2)
1.871(2)
1.868(2)
1.842(3)
1.885(3)
1.761(2)
1.871(2)
1.853(2)
1.865(2)
1.923(2)
1.957(2)
ω/deg
108.3(1)
108.9(1)
110.9(1)
110.0(1)
108.6(1)
110.2(1)
115.3(2)
109.1(1)
107.2(1)
108.9(2)
172.3(2)
108.9(1)
107.9(1)
110.4(1)
110.1(1)
110.7(1)
108.8(1)
115.5(1)
106.8(1)
109.2(1)
109.1(1)
172.8(1)
* Hereinafter, the geometric characteristics for another symꢀ
metrically independent molecule of complex 7 are given in paꢀ
rentheses.

Syntheses of tungsten carbyne complexes
Russ.Chem.Bull., Int.Ed., Vol. 52, No. 10, October, 2003
2143
Table 3. Selected bond lengths (d) and bond angles (ω) in
complex 7
The IR spectra were recorded on a PerkinꢀElmerꢀ577 specꢀ
trometer. Samples were prepared as Nujol mulls under argon.
1
The H, 13C, 29Si, and 119Sn NMR spectra were measured on a
Bruker DPXꢀ200 spectrometer with SiMe4 as the internal
standard.
The decomposition temperatures of the compounds syntheꢀ
sized were determined in evacuated sealed tubes and were not
corrected.
Bond
d/Å
Angle
ω/deg
W(1)—C(1)
W(1)—O(1)
W(1)—O(2)
W(1)—O(3)
Sn(1)—C(1)
Sn(1)—C(27)
W(2)—C(14)
W(2)—O(4)
W(2)—O(5)
W(2)—O(6)
Sn(1)—C(14)
Sn(1)—C(33)
1.759(3)
1.845(2)
1.862(2)
1.867(2)
2.107(3)
2.140(3)
1.762(3)
1.868(3)
1.869(2)
1.864(2)
2.111(3)
2.140(3)
C(1)—W(1)—O(1)
C(1)—W(1)—O(2)
C(1)—W(1)—O(3)
O(1)—W(1)—O(2)
O(1)—W(1)—O(3)
O(2)—W(1)—O(3)
C(1)—Sn(1)—C(14)
C(1)—Sn(1)—C(33)
109.5(1)
109.8(1)
109.1(1)
108.2(1)
110.0(1)
110.3(1)
113.5(1)
110.3(1)
The Xꢀray diffraction data sets were collected on an autoꢀ
mated Smart APEX diffractometer (λ MoꢀKα, ϕ—ω scan techꢀ
nique). The principal crystallographic characteristics and deꢀ
tails of Xꢀray data collection and structure refinement are given
in Table 4. All structures were solved by direct methods and
refined by the leastꢀsquares methods based on F 2 with anisoꢀ
C(14)—Sn(1)—C(33) 108.0(1)
hkl
W(1)—C(1)—Sn(1)
C(14)—W(2)—O(4)
C(14)—W(2)—O(5)
C(14)—W(2)—O(6)
O(4)—W(2)—O(5)
O(4)—W(2)—O(6)
O(5)—W(2)—O(6)
C(1)—Sn(1)—C(27)
170.6(2)
108.6(1)
107.7(1)
108.2(1)
109.5(1)
110.7(1)
112.1(1)
108.2(1)
tropic thermal parameters for all nonhydrogen atoms. The
H atoms in complexes 1, 2, and 7 were placed in geometrically
calculated positions and refined using the riding model. The
H atoms in complexes 5 and 6 were revealed from difference
Fourier syntheses and refined isotropically, except for the hydroꢀ
gen atoms at C(8) in molecule 5, which were placed in geoꢀ
metrically calculated positions and refined using the riding
model. In all the structures under study, high residual density
peaks (2.363—4.062 e•Å–3) were observed in the vicinity of the
W atoms due to high absorption, which was difficult to take into
account properly. All calculations were carried out using the
SHELXTL program package.14
C(14)—Sn(1)—C(27) 108.8(1)
C(33)—Sn(1)—C(27) 107.9(1)
W(2)—C(14)—Sn(1) 173.8(2)
Tris(tertꢀbutoxy)triphenylsilylmethylidinetungsten (3). A colꢀ
orless solution of Ph3SiC≡CPr (0.336 g, 1.029 mmol) in pentane
(5 mL) was added to a darkꢀred solution of W2(OBut)6 (0.829 g,
1.028 mmol) in pentane (10 mL). After storage at ∼20 °C for 1 h,
the reaction mixture turned paleꢀbrown. According to the
1H NMR spectroscopic data, the mixture contained only equivaꢀ
lent amounts of the Ph3SiC≡W(OBut)3 (3) and PrC≡W(OBut)3
(4) complexes. The pentane was removed by evaporation in
vacuo. Compound 4 was isolated from the solid residue by
vacuum sublimation (85—90 °C, 10–2—10–3 Torr, 1 h) as colorꢀ
less crystals in a yield of 0.394 g (83.65%). The results of 1H and
13C NMR spectroscopy are consistent with the data published in
the literature.15 After sublimation, the solid residue was recrysꢀ
tallized from pentane to prepare complex 3 in a yield of
0.528 g (80.00%) as colorless crystals, t.decomp. 113—115°C.
Found (%): C, 55.21; H, 6.56. C31H42O3SiW. Calculated (%):
C, 55.19; H, 6.28. IR, ν/cm–1: 3050, 1420, 1090, 730, 690, 470
(Ph3Si), 1150, 940 (W—O—C), 1350, 1235 (But). 1H NMR
(C6D6), δ: 1.08 (s, 27 H, But); 6.87—7.03 (m, 9 H, H(3), H(4));
of the Si (1.13 Å 5), Ge (1.19 Å 5), and Sn (1.36 Å 5)
atoms.
The W(1)—C(1)—Si(1), W(1)—C(1)—Ge(1), and
W(1)—C(1)—Sn(1) angles are 172.3(2)°, 172.8(1)°, and
170.6(2)° (173.7(2)°), respectively.
The sum of the covalent radii for the W atom (1.33 Å 5)
and the "triply bound" C atom (0.6 Å 6,7) is larger than the
experimental W≡C bond lengths (1.749(6)—1.785(7) Å).
We do not discuss the substantial, at first glance, differꢀ
ence in the W—C bond lengths in two independent molꢀ
ecules of complex 1 because of a poor accuracy of deterꢀ
mination of these distances (1.785(7) and 1.757(6) Å).
For the aboveꢀmentioned bond lengths, the confidence
intervals overlap with each other: 1.764—1.806 for
1.785(7) Å and 1.739—1.775 for 1.757(6) Å. Besides, the
crystal packing of complex 1 has no intermolecular conꢀ
tacts, which could be responsible for such a large differꢀ
ence in the distances of the same type in the indepenꢀ
dent molecules. In a few other compounds containing
the W≡C—Si fragments,8—11 the W—C and Si—C(Me)
distances are in the ranges of 1.739—1.769 and
1.835—1.875 Å, respectively.
7.62—7.67 (m, 6 H, H(2)). 13C NMR (C6D6), δ: 31.9 (CH3),
2
80.8 (WOCMe3, JC,
= 4.9 Hz); 127.9 (C(2)H); 129.4
183
W
1
(C(4)H); 136.7 (C(3)H); 138.9 (C(1)); 283.4 (W≡C, JC,
=
183
W
254.5 Hz).
Diphenyldi[tris(tertꢀbutoxy)tungstenmethylidino]silane (5).
A colorless solution of Ph2Si(C≡CPr)2 (0.257 g, 0.812 mmol) in
pentane (5 mL) was added to a darkꢀred solution of W2(OBut)6
(1.308 g, 1.622 mmol) in pentane (10 mL). After storage at
∼20 °C for 30 min, the reaction mixture turned paleꢀbrown.
According to the 1H NMR spectroscopic data, the mixture conꢀ
tained only the Ph2Si[C≡W(OBut)3]2 (5) and PrC≡W(OBut)3
(4) complexes. The pentane was removed by evaporation in
vacuo. Compound 4 was isolated from the solid residue by
vacuum sublimation (85—90 °C, 10–2—10–3 Torr, 1 h) in a
yield of 0.424 g (57.07%) as colorless crystals. The results of 1H
and 13C NMR spectroscopy are consistent with the data pubꢀ
Experimental
All operations were carried out in evacuated sealed tubes
and using the standard Schlenk techniques with the use of
thoroughly dried and degassed solvents. The starting reꢀ
agents W2(OBut)6,12 Ph3SiC≡CPr,13 Ph2Si(C≡CPr)2,13
13
Ph2Ge(C≡CPr)2,13 and Ph2Sn(C≡CPr)2
were prepared acꢀ
cording to known procedures.

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Safronova et al.
Table 4. Crystallographic data and details of structure refinement of complexes 1, 2, and 5—7
Parameter
1
2
5
6
7
Molecular formula
Molecular weight
Crystal dimensions/mm
T/K
C
31H42O3GeW C31H42O3SnW
C38H64O6GeW2
1012.68
0.4×0.3×0.1
100(2)
C38H64O6SnW2
1057.18
0.16×0.16×0.08
100(2)
C38H64O6SnW2
1103.28
0.2×0.15×0.1
100(2)
719.09
765.19
0.5×0.2×0.04
110(2)
0.5×0.3×0.2
110(2)
Space group
P21/n
P21/n
C2/c
C2/c
P21/n
a/Å
b/Å
c/Å
10.054(4)
31.930(12)
19.134(7)
92.707(8)
6135(4)
8
10.391(2)
16.155(4)
37.429(9)
92.499(5)
6277(2)
8
19.6827(12)
10.2214(6)
22.2890(14)
107.658(1)
4272.9(5)
4
19.6760(16)
10.2164(8)
22.3362(18)
107.429(2)
4283.8(6)
4
14.2480(13)
19.1022(17)
16.1153(15)
94.269(2)
4373.9(7)
4
β/deg
V/Å3
Z
dcalc/g cm–3
µ/cm–1
1.557
47.54
1.619
44.85
1.574
54.47
1.639
60.93
1.675
58.51
Absorption correction
Tmin/Tmax
F(000)
SADABS program
0.2193/0.6119
2008
0.194/0.493
2864
0.1505/0.3577
3008
0.4423/0.9522
2080
0.3874/0.5923
2152
2θmax/deg
54
60
58
58
58
Number of independent
13367
18288
5518
5604
11607
reflections (Rint
)
(0.1628)
0.0574
(8665)
0.1299
(0.0702)
0.0570
(11188)
0.1455
(0.029)
0.033
(5216)
0.0944
(0.0308)
0.0289
(5401)
0.0714
(0.0482)
0.0272
(10091)
0.0687
R1 (based on F for reflections
with I > 2σ(I ))
wR2 (based on F 2 for
all reflections)
Number of parameters
in the refinement
Weighting scheme
α
649
649
338
341
424
2
2
2
w
–1=σ (Fo2)+(αP)2+βP, where P = 1/3(Fo + 2Fc
)
0.0511
0
0.0724
0.0583P
15.8020
0.0366
7.0235
0.0315
6.8071
β
0
GOOF
0.922
0.996
1.094
1.099
1.061
Residual electron
density peaks/Å–3
–2.144/3.038
–1.659/3.441
–3.216/4.062
–2.902/2.363
–1.237/2.426
,
emin/emax
lished in the literature.15 After sublimation, the solid residue was
recrystallized from pentane to prepare complex 5 in a yield of
0.394 g (47.99%) as colorless crystals, t.decomp. 112—115 °C.
Found (%): C, 45.03; H, 6.34. C38H64O6SiW2. Calculated (%):
C, 45.07; H, 6.37. IR, ν/cm–1: 1440, 1070, 730, 695, 455 (Ph2Si),
1150, 940 (W—O—C), 1350, 1230 (But). 1H NMR (tolueneꢀ
d8), δ: 1.40 (s, 54 H, But); 7.23—7.36 (m, 6 H, H(3), H(4));
H(4)); 8.02—8.07 (m, 4 H, H(2)). 13C NMR (tolueneꢀd8), δ:
32.2 (CH3); 79.9 (WOCMe3, 2JC, W = 4.9 Hz); 127.3 (C(3)H);
183
128.6 (C(4)H); 136.0 (C(2)H); 145.3 (C(1)); 279.9 (W≡C,
1JC, W = 271.6 Hz).
183
Diphenyldi[tris(tertꢀbutoxy)tungstenmethylidino]stannane
(7). Complex 7 was synthesized and isolated as described above.
Compound
4
was prepared from (ButO)6W2 (1.285 g,
8.12—8.16 (m, 4 H, H(2)). 13C NMR (tolueneꢀd8), δ: 32.3
1.594 mmol) and Ph2Sn(C≡CPr)2 (0.325 g, 0.798 mmol) in a
2
1
(CH3), 80.3 (WOCMe3, JC,
= 4.9 Hz); 127.3 (C(2)H);
yield of 0.397 g (54.38%) as colorless crystals (the results of H
183
W
137.1 (C(3)H); 128.8 (C(4)H); 143.2 (C(1)); 290.1 (W≡C,
and 13C NMR spectroscopy are in agreement with the data
published in the literature15). Complex 7 was isolated in a yield
of 0.615 g (69.97%) as colorless crystals, t.decomp. 112—114 °C.
Found (%): C, 41.34; H, 5.82. C38H64O6SnW2. Calculated (%):
C, 41.37; H, 5.85. IR, ν/cm–1: 1435, 1060, 720, 690, 445
(Ph2Sn), 1150, 945 (W—O—C), 1350, 1230 (But). 1H NMR
(tolueneꢀd8), δ: 1.42 (s, 54 H, But); 7.20—7.35 (m, 6 H, H(3),
H(4)); 7.95—7.98 (m, 4 H, H(2)). 13C NMR (tolueneꢀd8), δ:
1JC, W = 251.2 Hz). 29Si NMR (tolueneꢀd8), δ: –53.2
183
Diphenyldi[tris(tertꢀbutoxy)tungstenmethylidino]germane (6).
Complex 6 was synthesized and isolated as described above.
Compound
4
was prepared from (ButO)6W2 (1.700 g,
2.108 mmol) and Ph2Ge(C≡CPr)2 (0.381 g, 1.055 mmol) in a
1
yield of 0.798 g (82.61%) as colorless crystals (the results of H
and 13C NMR spectroscopy are identical with the data pubꢀ
lished in the literature15). Complex 6 was isolated in a yield of
0.829 g (74.39%) as colorless crystals, t.decomp. 102—104 °C.
Found (%): C, 43.21; H, 6.12. C38H64O6GeW2. Calculated (%):
C, 43.17; H, 6.10. IR, ν/cm–1: 1440, 1070, 730, 695, 455
(Ph2Ge), 1150, 940 (W—O—C), 1350, 1230 (But). 1H NMR
(tolueneꢀd8), δ: 1.39 (s, 54 H, But); 7.22—7.36 (m, 6 H, H(3),
32.0 (CH3); 79.3 (WOCMe3, 2JC, W = 4.4 Hz); 128.4 (C(2)H,
183
2JC, Sn = 53.0 Hz, 2JC, Sn = 54.9 Hz); 128.7 (C(4)H, 4JC,Sn
12.2 Hz); 137.6 (C(3)H, JC,Sn = 39.9 Hz), 146.7 (C(1),
=
117
119
3
1
1JC,
= 537.5 Hz, JC,
= 562.2 Hz); 277.0 (W≡CSn,
117
119
Sn
Sn
1JC, W = 270.7 Hz, 1JC, Sn = 247.8 Hz, 1JC, Sn = 259.5 Hz).
119Sn NMR (tolueneꢀd8), δ: –258.7 (2J119
183
117
117
W = 732.2 Hz).
183
Sn,

Syntheses of tungsten carbyne complexes
Russ.Chem.Bull., Int.Ed., Vol. 52, No. 10, October, 2003
2145
8. L. Giannini, E. Solari, S. Dovesi, C. Floriani, N. Re,
A. ChiesiꢀVilla, and C. Rizzoli, J. Am. Chem. Soc., 1999,
121, 2784.
9. S. W. Seidel, R. R. Schrock, and W. M. Davis, Organometalꢀ
lics, 1998, 17, 1058.
This study was financially supported by the Russian
Foundation for Basic Research (Project Nos. 02ꢀ03ꢀ32113
and 00ꢀ03ꢀ40116).
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Received December 19, 2002;
in revised form April 29, 2003