Synthesis, structures and catalytic properties of germanium-containing tungsten alkylidene complex Me3Ge-CH{double bond, long}W(NAr)(OR)2 and metallacycle [CH(GeMe3)CH(GeMe3)CH2]W(NAr)(OR)2

Article abstract of DOI:10.1016/j.jorganchem.2006.08.029

Alkylidene complex of tungsten Me₃Ge-CH{double bond, long}W(NAr)(OCMe₂CF₃)₂ (1) (Ar = 2, 6 - Pr₂ⁱ C₆ H₃) has been prepared by the reaction of Me₃GeCH{double bond, long}CH₂ with known alkylidene compound Bu^t-CH{double bond, long}Mo(NAr)(OCMe₂CF₃)₂ at a molar ratio 1:1. Metallacycle [CH(GeMe₃)CH(GeMe₃)CH₂]W(NAr)(OCMe₂CF₃)₂ (2) was isolated from the same reaction when twofold excess of Me₃GeCH{double bond, long}CH₂ was used. The both compounds 1 and 2 were structurally characterized. They were found to have low activity in metathesis of 1-hexene and high activity in ROMP of cyclooctene and norbornene.

Full text of DOI:10.1016/j.jorganchem.2006.08.029

Journal of Organometallic Chemistry 691 (2006) 5240–5245
www.elsevier.com/locate/jorganchem
Synthesis, structures and catalytic properties of
germanium-containing tungsten alkylidene complex
Me3Ge-CH@W(NAr)(OR)2 and metallacycle
[CH(GeMe3)CH(GeMe3)CH2]W(NAr)(OR)2
*
Leonid N. Bochkarev , Yulia E. Begantsova, Andrey L. Bochkarev, Natalia E. Stolyarova,
Irina K. Grigorieva, Irina P. Malysheva, Galina V. Basova, Elena O. Platonova,
Georgii K. Fukin, Evgenii V. Baranov, Yurii A. Kurskii, Gleb A. Abakumov
G.A. Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences, Tropinina 49, Nizhny Novgorod 603950, Russian Federation
Received 27 June 2006; received in revised form 14 August 2006; accepted 14 August 2006
Available online 22 August 2006
Abstract
Alkylidene complex of tungsten Me3Ge-CH@W(NAr)(OCMe2CF3)2 (1) ðAr ¼ 2; 6-Pri2C6H3Þ has been prepared by the reaction of
Me3GeCH@CH2 with known alkylidene compound But–CH@Mo(NAr)(OCMe2CF3)2 at a molar ratio 1:1. Metallacycle [CH(Ge-
Me3)CH(GeMe3)CH2]W(NAr)(OCMe2CF3)2 (2) was isolated from the same reaction when twofold excess of Me3GeCH@CH2 was used.
The both compounds 1 and 2 were structurally characterized. They were found to have low activity in metathesis of 1-hexene and high
activity in ROMP of cyclooctene and norbornene.
ꢀ 2006 Published by Elsevier B.V.
Keywords: Alkylidene complexes; Metallacycle; Tungsten; Germanium; Synthesis; Structure elucidation; Olefin metathesis; Catalytic activity
1. Introduction
Herein, we report the synthesis of the trimethylgermyl-
containing tungsten alkylidene complex 1 and also metalla-
cycle 2 and their catalytic properties in metathesis of
1-hexene and ROMP of cyclooctene and norbornene.
Synthesis and catalytic properties of molybdenum and
tungsten alkylidene complexes of the type Alkyl
–CH@M(NAr)(OR0)2 (M = Mo, W; Alkyl = But, PhMe2C;
Ar = 2,6-i-Pr2C6H3; R0 = But, CMe2CF3, CMe(CF3)2) in
olefin metathesis reactions are well documented [1]. Much
less known about similar molybdenum and tungsten com-
pounds with heteroelement-containing substituents
attached to carbene carbon [2]. We have recently found
that catalytic activity of silicon- and germanium-containing
alkylidene complexes of molybdenum R3E–CH@Mo-
(NAr)(OCMe2CF3)2 (E = Si, Ge; R = Me, Ph) in metathe-
sis of 1-hexene depended essentially on the nature of substi-
tuent bonded to carbene carbon atom [3].
2. Results and discussion
For preparation of alkylidene complex 1 we used the
known synthetic route, developed originally for prepara-
tion of silicon-containing alkylidene complexes of molyb-
denum [2a] and tungsten [2b]:
ButACH@WðNArÞðOCMe2CF3Þ2 þ Me3GeCH@CH2
Benzene
! 1 þ ButACH@CH2
The course of the reactions was monitored by 1H NMR.
After completion of the reaction (5 h, at room temperature)
the complex 1 was isolated as unstable in air bright-yellow
*
Corresponding author. Tel.: +7 8312 627010; fax: +7 8312 627497.
E-mail address: lnb@iomc.ras.ru (L.N. Bochkarev).
0022-328X/$ - see front matter ꢀ 2006 Published by Elsevier B.V.
doi:10.1016/j.jorganchem.2006.08.029

L.N. Bochkarev et al. / Journal of Organometallic Chemistry 691 (2006) 5240–5245
5241
crystals. Characteristic Ha and Ca signals were found in
NMR spectra at 9.57 ppm and 231.8 ppmr respectively. It
should be noted that in benzene-d6 complex 1 decomposed
completely at room temperature within 5 days. According
to X-ray data the complex 1 have a syn-conformation.
The W and Ge atoms have a typical tetrahedral coordina-
tion environment (Fig. 1) the same as in early published
Me3E–CH@Mo(NAr)(OCMe2CF3)2 (E = Si, Ge) com-
plexes [2a–4].
phenyl alkylidene complexes (Mo–C–Si – 144.8(2)ꢁ, Mo–
C–Ge – 144.1(1)ꢁ). Apparently it is due to the different size
of the Ph3E and Me3E ligands.
The reaction of But–CH@W(NAr)(OR0)2 with two
equivalents of trimethylvinylgermane afforded the metalla-
cycle 2:
ButACH@WðNArÞðOCMe2CF3Þ þ 2Me3GeCH@CH2
2
Benzene
! 2 þ ButACH@CH2
All distances at W atom are practically equal to the anal-
ogous ones in Me3E–CH@Mo(NAr)(OCMe2CF3)2 (E = Si,
Ge) complexes. The W(1)C(1)Ge(1) angle of 137.7(2)ꢁ is
also very close to those angles in alkylidene complexes of
molybdenum [E = Si (138.5(1)ꢁ, Ge(137.6(1)ꢁ]. Thus, there
are no significant differences in the geometric parameters
of 1 and Me3E–CH@Mo(NAr)(OCMe2CF3)2 (E = Si, Ge)
complexes. However, some difference between the complexes
Me3E–CH@M(NAr)(OCMe2CF3)2 (M = Mo, W; E = Si,
Ge) and Ph3E–CH@Mo(NAr)(OCMe2CF3)2 (E = Si, Ge)
[3,4] should be noted. The bond angles M–C–E (M = Mo,
W; E = Si, Ge) in the methyl alkylidene complexes (Mo–
C–Si – 138.5(1)ꢁ, Mo–C–Ge – 137.57(10)ꢁ, W–C–Ge –
137.7(2)ꢁ) are noticeably smaller than in the analogous
Compound 2 was isolated as unstable in air light-brown
crystals. In C6D6 it dissociates with the formation of equi-
librium mixture containing 1, Me3GeCH@CH2 and 2 in
approximately equal amount. According to the X-ray data
the W(1) atom has a distorted trigonal bipyramidal coordi-
nation (Fig. 2). The C(1), C(9) atoms of tungstacyclobutane
ring and OCMe2CF3 ligand occupy equatorial positions
whereas other alkoxide ligand and imido function are
placed in apical sites. The spatial configuration of 2 is quite
similar to that of the [CH(SiMe3)CH(SiMe3)CH2]W(NAr)-
(OCMe(CF3)2)2 compound (2a) [2b] and differs somewhat
from spatial configuration of [CH2CH2CH2]W(NAr)-
(OC(CF2CF2CF3)(CF3)2)2 complex (2b) [2b].
Fig. 2. Molecular structure of complex 2 (30% probability thermal
˚
ellipsoids). Selected bond lengths (A) and angles (ꢁ): W(1)–N(1) 1.769(3),
W(1)–O(1) 1.983(2), W(1)–O(2) 1.924(3), W(1)–C(1) 2.058(4), W(1)–C(9)
2.079(4), W(1)–C(5) 2.354(4), Ge(1)–C(2) 1.930(6), Ge(1)–C(3) 1.931(5),
Ge(1)–C(4) 1.954(5), Ge(1)–C(1) 1.971(4), Ge(2)–C(6) 1.931(6), Ge(2)–
C(8) 1.942(5), Ge(2)–C(7) 1.954(6), Ge(2)–C(5) 1.980(4), O(1)–C(10)
1.406(5), O(2)–C(14) 1.420(5), N(1)–C(18) 1.390(3); N(1)–W(1)–O(2)
97.94(13), N(1)–W(1)–O(1) 173.66(14), O(2)–W(1)–O(1) 83.27(11), N(1)–
W(1)–C(1) 92.80(15), O(2)–W(1)–C(1) 134.70(14), O(1)–W(1)–C(1)
90.71(13), N(1)–W(1)–C(9) 90.99(15), O(2)–W(1)–C(9) 141.04(15), O(1)–
W(1)–C(9) 84.26(14), C(1)–W(1)–C(9) 82.12(16), N(1)–W(1)–C(5)
99.44(14), O(2)–W(1)–C(5) 162.39(12), O(1)–W(1)–C(5) 79.76(12), C(1)–
W(1)–C(5) 41.57(16), C(9)–W(1)–C(5) 41.51(15).
Fig. 1. Molecular structure of complex 1 (30% probability thermal
ellipsoids). Selected bond lengths (A) and angles (ꢁ): W(1)–N(1) 1.739(3),
˚
W(1)–C(1) 1.882(3), W(1)–O(2) 1.893(2), W(1)–O(1) 1.895(2), Ge(1)–C(1)
1.927(4), Ge(1)–C(2) 1.934(4), Ge(1)–C(3) 1.924(5), Ge(1)–C(4) 1.924(4),
N(1)–C(13) 1.394(4); N(1)–W(1)–C(1) 103.7(1), N(1)–W(1)–O(2) 112.8(1),
C(1)–W(1)–O(2) 108.7(1), N(1)–W(1)–O(1) 111.7(1), C(1)–W(1)–O(1)
110.5(1), O(2)–W(1)–O(1) 109.2(1), C(4)–Ge(1)–C(3) 111.9(2), C(4)–
Ge(1)–C(1) 109.4(2), C(3)–Ge(1)–C(1) 109.1(2), C(4)–Ge(1)–C(2)
107.4(2), C(3)–Ge(1)–C(2) 109.5(2), C(1)–Ge(1)–C(2) 109.5(2), C(13)–
N(1)–W(1) 169.2(2), W(1)–C(1)–Ge(1) 137.7(2).

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L.N. Bochkarev et al. / Journal of Organometallic Chemistry 691 (2006) 5240–5245
The four-membered –W(1)–C(1)–C(5)–C(9)– metallacy-
2a (149.3(8)ꢁ) and to 2b (172.4(13)ꢁ). The same tendency is
also observed for equatorial W–O–C angles (136.5(2)ꢁ in 2,
140.4(9)ꢁ in 2a and 146.6(11)ꢁ in 2b). In fact this tendency
reflects both the increase of electronegativity of alkoxide
ligands in 2–2b and the change of their steric sizes.
The alkylidene complex 1 and metallacycle 2 were found
to reveal low catalytic activity in metathesis of neat 1-hex-
ene. The rate constants (0.5 · 10ꢀ5 L molꢀ1 sꢀ1 and 1.8 ·
10ꢀ5 L molꢀ1 sꢀ1 for 1 and 2, respectively) are one order
of magnitude lesser than rate constant (1.73 ·
10ꢀ4 L molꢀ1 sꢀ1) of the same reaction with similar germa-
nium-containing molybdenum alkylidene complex Me3Ge–
CH@Mo(NAr)(OCMe2CF3)2 as catalyst [3].
Ring opening polymerization of cyclooctene and nor-
bornene initiated by complex 1 and metallacycle 2 proceeds
readily at room temperature. The polyoctenylenes formed
were found to have predominantly trans configuration
while polynorbornenes – predominantly cis configuration.
Some characteristics of polymeric materials are presented
in Table 1. Unfortunately we so far could not determine
the molecular weights of the polyoctenylenes because of
their insufficient solubility in THF, CHCl3 and other com-
mon organic solvents necessary for GPC experiments.
cle in 2 is bent. The dihedral angle between W(1)C(1)C9)
and C(1)C(5)C(9) planes is 20.1ꢁ that is a significantly smal-
ler than in 2a (29.9ꢁ) whereas the same metallacycle in 2b is
absolutely flat. The GeMe3 groups in 2 (the same as SiMe3
groups in 2a) occupy a trans-positions relatively to each
other, thus minimizing a non-bonding repulsion between
them. Apparently steric factors in tungstacyclobutane ring
in 2 lead to the distortion of metallacycle from the planarity.
It should be noted that in complexes [CH2CHButCH2]-
W(NAr)(OCMe2(CF3))2 [5] and [CHButCH2CH2(CO2-
Me)]W(NAr)(OCMe2(CF3))2 [6], which also contain
substituents in tungstacyclobutane rings, the metallacycles
are also bent.
A low quality of the X-ray data obtained for 2a and 2b
prevent a proper comparison of WC3 geometry in 2a and
2b with that in 2 (Fig. 3). However, it can be noted that
˚
the bond length W(1)–N(1) in 2 (1.769(3) A) is noticeably
˚
longer than analogous distance in 2a (1.738(9) A).
The W. . .C distances in complexes [CH2CHButCH2]W-
(NAr)(OCMe2(CF3))2 (2.79(1) A), [CHButCH2CH2
˚
˚
(CO2Me)]W(NAr)(OCMe2(CF3))2 (2.772(8) A) are signifi-
cantly longer than those in 2–2b.
˚
˚
The equatorial (1.983(2) A) and axial (1.924(3) A) W–
O(1,2) distances in 2 are distinctly different. The equatorial
alkoxide ligand in 2 is bent away from the imido ligand.
The N(1)W(1)O(2) angle in 2 is 97.9(1)ꢁ. The same situa-
tion is observed in 2a (97.3(4)ꢁ). The analogous angle in
2b is significantly bigger (102.1(6)ꢁ). It is interesting to note
that the axial W–O–C angle increase from 2 (141.0(3)ꢁ) to
3. Experimental
3.1. General
All manipulations were carried out in evacuated sealed
ampoules using standard Schlenk techniques. The solvents
C(5)
C
C
1.536(31)
C
1.625(15)
C
1.606(16)
1.584(29)
C
1.592(6)
C(9)
1.590(6)
C(1)
C
2.058(4)
2.099(11)
2.042(20)
2.064(22)
2.066(11)
2.079(4)
W
W
W(1)
C(1)W(1)C(9) 82.12(16)
W(1)C(1)C(5) 79.3(2)
W(1)C(9)C(5) 78.5(2)
C(1)C(5)C(9) 117.3(3)
82.3(4)
79.4(6)
78.0(6)
116.1(8)
82.4(8)
78.6(12)
78.9(13)
120.1(18)
2
2a
2b
Fig. 3. The geometry of WC3 fragments in 2–2b.
Table 1
Some characteristics of obtained polymers
Catalyst
Monomer
Conversion (%)
Cis:trans ratio
Mw
Mn
PDI
Tm (ꢁC)
1
Cyclooctenea
Norborneneb
Cyclooctenec
Norbornened
88
75
92
78
11:89
86:14
17:83
84:16
63.0 0.3
57.6 0.4
49.6 0.1
60.0 0.1
368600
81300
175300
42300
2.10
1.92
2
a
[Monomer]:[Catalyst] = 100.
[Monomer]:[Catalyst] = 250.
[Monomer]:[Catalyst] = 43.
[Monomer]:[Catalyst] = 182.
b
c
d

L.N. Bochkarev et al. / Journal of Organometallic Chemistry 691 (2006) 5240–5245
5243
were thoroughly dried and degassed. Compound But–
CH@W(NAr)(OCMe2CF3)2 [2c] and Me3GeCH@CH2 [7]
were prepared according to a literature procedure. 1H
NMR and 13C NMR spectra were recorded on a Bruker
DPX-200 NMR spectrometer. The chemical shifts are
reported in parts per million with tetramethylsilane
(0.00 ppm) as the internal standard. The molecular-weight
distribution (MWD) of polynorbornenes was determined
by gel-permeation chromatography (GPC) using a set of
five styrogel columns with a pore diameter of 1 · 105,
3 · 10 , 1 · 10 , 1 · 10 and, 250 A (Waters, USA). The
detector was an R-403 differential refractometer (Waters),
and the eluent was tetrahydrofuran. Narrow-MWD poly-
styrene references were used for calibration. The contents
of cis and trans units in the polymers were determined by
1H and 13C NMR spectroscopy according to a literature
procedure [8–10]. Melting temperatures of the polymers
were determined using differential scanning calorimeter
(NETZSCH DSC 204 F1) using a first heating rate of
10 ꢁC/min from 10 to 80 ꢁC.
and 10.0 Hz, aCHH0), 4.12–4.00 (m 4H, aCHH0, aCH-
GeMe3, CHMe2), 1.61 (d, 6H, OCMe2CF3), 1.51 (d, 6H,
OCMe2CF3), 1.26 (m, 12H, CHMe2), 0.47 (s, 9H, GeMe3),
0.06 (s, 9H, GeMe3), ꢀ0.74 (q, 1H, J ꢁ 9.9 Hz,
bCHGeMe3).
3.4. Metathesis of 1-hexene
The kinetic experiments and determinations of rate con-
stants were performed as described in the literature
[3,11,12]. In a typical experiment to an ampoule containing
35.8 mg of catalyst and connected with gas burette 1.234 g
(1.46 mL) of neat 1-hexene was added in argon atmo-
sphere. The mixture was stirred magnetically. Amount of
ethylene was determined volumometrically.
4
4
3
˚
3.5. Polymerization of cyclooctene
To an ampoule containing 0.045 g (0.061 mmol) of cat-
alyst 1 0.68 g (6.1 mmol) of cyclooctene was added at
room temperature. The mixture was magnetically stirred
and in a less than a minute became light-orange transpar-
ent solid. The polyoctenylene formed was purified three
times by precipitation by methanol from CHCl3 and dried
in vacuum at room temperature until the weight was not
changed. The yield was 0.59 g (88%). Polymerization of
cyclooctene using compound 2 as catalyst was carried
out in similar manner. The polymerization time was 2 h.
From 0.42 g (3.8 mmol) of cyclooctene and 0.08 g
(0.090 mmol) of catalyst 2 0.40 g (92%) of polyoctenylene
was obtained.
3.2. Preparation of (2,6-diisopropylphenylimido)-bis(1,1-
dimethyl-2,2,2-trifluoroethanolato)-
(trimethylgermylmethylidene)-tungsten (1)
A solution of Me3GeCH@CH2 (0.20 g, 1.38 mmol) in
2 mL of benzene was added to a solution of But–
CH@W(NAr)(OCMe2CF3)2 (1.0 g, 1.46 mmol) in 3 mL of
benzene. The reaction mixture was kept at room tempera-
ture for 5 h. Evaporation of the solvent and volatiles in
vacuo and crystallization of the solid residue from pentane
afforded 0.49 g (45.0%) of 1 as bright-yellow crystals. Anal.
Calc. for C24H39F6GeNO2W: C, 38.75; H, 5.28. Found: C,
38.87; H, 5.21%. 1H NMR (200 MHz, C6D6) d 9.57 (s, 1H,
WCHGeMe3), 7.20–6.90 (m, 3H, Harom), 3.67 (sept, 2H,
CHMe2), 1.34 and 1.26 (s, 6H each, OCMe2CF3), 1.24
(d, 12H, CHMe2), 0.23 (s, 9H, WCHGeMe3). 13C NMR
(50 MHz, C6D6) d 231.8 (WCHGeMe3), 152.5 (Cipso),
144.7 (Co), 127.1 (q, JCF = 285 Hz, CF3), 126.6 (Cp),
3.6. Polymerization of norbornene
To an ampoule containing 0.0297 g (0.040 mmol) of cat-
alyst 1 in 2 mL of benzene 0.94 g (10.0 mmol) of norborn-
ene in 3 mL of benzene was added at room temperature.
The mixture was magnetically stirred and in less than a
minute became light-orange transparent viscous and after
that the polynorbornene formed was purified three times
by precipitation by methanol from CHCl3 and dried in vac-
uum at room temperature until the weight was not chan-
ged. The yield was 0.71 g (75%). Polymerization of
norbornene using compound 2 as catalyst was carried out
in similar manner. The polymerization time was 2 min.
From 0.65 g (6.9 mmol) of norbornene and 0.0344 g
(0.039 mmol) of catalyst 2 0.51 g (78%) of polynorbornene
was obtained.
2
122.8 (Cm), 79.9 (q, JCF = 28.8 Hz, OCMe2CF3), 28.2
(OCMe MeCF3), 24.6 (CHMe2), 24.1 (OCMeMeCF3),
23.7 (CHMe2), 1.4 (MoCHGeMe3).
3.3. Preparation of 1-(2,6-diisopropylphenylimido)-1,1-
bis(1,1-dimethyl-2,2,2-trifluoroethanolato)-2,3-
bis(trimethylgermyl)-1-tungstacyclobutane (2)
A solution of Me3GeCH@CH2 (0.65 g, 4.46 mmol) in
2 mL of benzene was added to a solution of But–
CH@W(NAr)(OCMe2CF3)2 (1.5 g, 2.19 mmol) in 5 mL of
benzene. The reaction mixture was kept at room tempera-
ture for 5 h. Slow evaporation of the solvent and volatiles
in vacuo at room temperature led to the formation of
light-brown crystals of 2. The isolated yield was 1.17 g
(60.0%). Anal. Calc. for C29H51F6Ge2NO2W: C, 39.19;
3.7. Crystallographic data for 1 and 2
The data were collected on a Bruker AXS ‘‘SMART
APEX’’ diffractometer (graphite-monochromator, Mo
˚
Ka-radiation, u ꢀ x-scan technique, k = 0.71073 A). The
intensity data were integrated in the SAINT program [13].
SADABS [14] was used to perform area-detector scaling and
absorption corrections. The structures were solved by
1
H, 5.74. Found: C, 39.17; H, 5.77%. H NMR (200 MHz,
C6D6) 7.00–6.65 (m, 3H, Harom), 5.43 (m, 1H, JHH = 4.8

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L.N. Bochkarev et al. / Journal of Organometallic Chemistry 691 (2006) 5240–5245
Table 2
The details of crystallographic, collection and refinement data for 1 and 2
1
2
Empirical formula
Formula weight
Temperature (K)
Crystal system
Space group
C24H39F6GeNO2W
744.00
100(2)
Monoclinic
P2(1)/c
10.2484(6)
30.7012(19)
C29H51F6Ge2NO2W
888.74
100(2)
Monoclinic
P2(1)/n
17.8086(9)
11.9442(6)
˚
a (A)
˚
b (A)
˚
c (A)
10.6441(7)
18.3515(10)
b (ꢁ)
Volume (A )
118.570(1)
2941.2(3)
112.711(1)
3600.9(3)
3
˚
Z
4
4
Density (calculated) (g/cm3)
Absorption coefficient (mmꢀ1
F(000)
1.680
4.988
1464
1.639
4.901
1760
)
Crystal size (mm)
0.22 · 0.06 · 0.03
0.34 · 0.15 · 0.14
hmax Range for data collection ꢁ
Index ranges
Reflections collected
29.12
26.00
ꢀ14 6 h 6 13, ꢀ41 6 k 6 42, ꢀ14 6 l 6 14
ꢀ14 6 h 6 21, ꢀ14 6 k 6 14, ꢀ22 6 l 6 22
30808
21043
Independent reflections [Rint
]
7830 [0.0327]
7067 [0.0286]
Absorption correction
SADABS
Maximum/minimum transmission
Refinement method
Data/restraints/parameters
Goodness-of-fit on F2
0.8648/0.4067
0.5470/0.2866
Full-matrix least-squares on F2
7830/0/320
7067/20/358
1.038
1.102
Final R indices [I > 2r(I)]
R indices (all data)
Largest difference in peak and hole (e A
R1 = 0.0341, wR2 = 0.0792
R1 = 0.0417, wR2 = 0.0819
2.343 and ꢀ1.301
R1 = 0.0408, wR2 = 0.0983
R1 = 0.0477, wR2 = 0.1010
2.422 and ꢀ1.044
ꢀ3
˚
)
direct methods and were refined on F2 using all reflections
with SHELXTL package [15]. All non-hydrogen atoms were
refined anisotropically. The hydrogen atoms in 1 and 2
were placed in calculated positions and refined in the ‘‘rid-
ing-model’’. The details of crystallographic, collection and
refinement data are shown in the Table 2. CCDC-611758 1
and 611759 2 contain the supplementary crystallographic
data for this paper. These data can be obtained free of
charge at www.ccdc.cam.ac.uk/const/retrieving.html [or
from the Cambridge Crystallographic Data Centre, 12
Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223/
336 033; e-mail: deposit@ccdc.cam.ac.uk].
(e) M.R. Buchmeiser, Chem. Rev. 100 (2000) 1565;
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Acknowledgements
[3] L.N. Bochkarev, Yu.E. Begantsova, V.I. Shcherbakov, N.E. Stolyar-
ova, I.K. Grigorieva, I.P. Malysheva, G.V. Basova, A.L. Bochkarev,
Yu.P. Barinova, G.K. Fukin, E.V. Baranov, Yu.A. Kurskii, G.A.
Abakumov, J. Organomet. Chem. 690 (2005) 5720.
[4] L.N. Bochkarev, A.V. Nikitinskii, Y.E. Begantsova, V.I. Shcherba-
kov, N.E. Stolyarova, I.K. Grigorieva, I.P. Malysheva, G.V. Basova,
G.K. Fukin, E.V. Baranov, Yu.A. Kurskii, G.A. Abakumov, J.
Organomet. Chem. 690 (2005) 3212.
This work was supported by the Russian Foundation
for Basic Research (Project Nos. 05-03-32694 and 06-03-
32728) and by the Grant of President of Russian Federa-
tion (Project MK
– 1832.2005.3 and Project NSh
8017.2006.3). The authors thank Mrs. A.V. Arapova for
DSC analysis of polymeric materials.
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[6] J. Feldman, J.S. Murdzek, W.M. Davis, R.R. Schrock, Organomet-
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