Molybdenum tin-containing π-complexes (R3SnCH=CH 2)Mo(N-2,6-Pr2i-C6H 3)(OCMe2CF3)2. Synthesis and catalytic properties

Article abstract of DOI:10.1134/S1070363212010033

The tin-containing molybdenum π-complexes (R₃SnCH=CH ₂)Mo(N-2,6-Pr_2iC₆H ₃)(OCMe₂CF₃)₂ (R = Me, Et, Ph) were synthesized by reaction of PhMe₂CCH=Mo(N-2,6-Pr₂ ⁱC₆H₃)(OCMe₂CF₃) ₂ with organotin vinyl reagents R₃SnCH=CH₂. The structure of compounds I-III was determined by NMR spectroscopy. Complexes I-III are active initiators of the norbornene metathesis polymerization.

Full text of DOI:10.1134/S1070363212010033

ISSN 1070-3632, Russian Journal of General Chemistry, 2012, Vol. 82, No. 1, pp. 17–22. © Pleiades Publishing, Ltd., 2012.
Original Russian Text © Yu.P. Barinova, L.N. Bochkarev, Yu.A. Kurskii, G.A. Abakumov, 2012, published in Zhurnal Obshchei Khimii, 2012, Vol. 82, No. 1,
pp. 20–25.
Molybdenum Tin-containing π-Complexes
(R3SnCH=CH2)Mo(N-2,6-Pr2i-C6H3)(OCMe2CF3)2.
Synthesis and Catalytic Properties
Yu. P. Barinova, L. N. Bochkarev, Yu. A. Kurskii, and G. A. Abakumov
Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences,
Tropinina 49, Nizhny Novgorod, 603950 Russia
e-mail: lnb@iomc.ras.ru
Received November 1, 2010
Abstract—The tin-containing molybdenum π-complexes (R3SnCH=CH2)Mo(N-2,6-Pri2C6H3)(OCMe2CF3)2 (R =
Me, Et, Ph) were synthesized by reaction of PhMe2CCH=Mo(N-2,6-Pri2C6H3)(OCMe2CF3)2 with organotin
vinyl reagents R3SnCH=CH2. The structure of compounds I–III was determined by NMR spectroscopy.
Complexes I–III are active initiators of the norbornene metathesis polymerization.
DOI: 10.1134/S1070363212010033
Reaction of the molybdenum alkylidene com-
pounds AlkylC(H)=Mo(N-2,6-Pri2C6H3)(OCMe2CF3)2
Mo(N-2,6-Pri2C6H3)(OCMe2CF3)2 [2]. In this study we
found that the reaction of alkylidene compound
PhMe2CC(H)=Mo(N-2,6-Pri2C6H3)(OCMe2CF3)2 with
organotin vinyl reagents R3SnCH=CH2 (R=Me, Et,
Ph) also led to the formation of molybdenum π-
complexes.
(Alkyl
=
t-Bu, PhMe2C) with vinylsilanes
R3SiCH=CH2 (R=Me, Et, Ph ) is known to afford
silicon-containing carbene complexes R3SiC(H)=
Mo(N-2,6-Pri2C6H3)(OCMe2CF3)2 [1–3]. Similarly
proceeds the interaction of the molybdenum alkylidene
compounds with trimethylvinylgermane and tri-
phenylvinylgermane [4]. Recently we found that the
reaction of PhMe2CCH=Mo(N-2,6-Pri2C6H3)(OCMe2CF3)2
with triethylvinylgermane proceeded in another
direction and led to the formation of germanium-
containing molybdenum π-complex (Et3GeCH=CH2)·
Reaction of PhMe2CC(H)=Mo(N-2,6-Pri2C6H3)·
(OCMe2CF3)2 with triorganylvinylstannanes proceeds
at room temperature over 5–10 min, and leads to the
formation of π-complexes (CF3Me2CO)2(N-2,6-
Pri2C6H3)Mo(CH2=CH-SnR3) and asymmetric tin-con-
taining olefin derivatives:
PhMe2CCH=Mo(N-2,6-Pr2i-C6H3)(OCMe2CF3)2 + 2 R3SnCH=CH2
C6D6, 20°C
(CF3Me2CO)2(C6H3-Pr2i-2,6-N)Mo(CH2=CHSnR3) + PhMe2CCH=CHCH2SnR3,
R = Me (I), Et (II), Ph (III).
1
After the reaction completion, the 1H NMR
spectrum of the reaction mixture does not contain
signals of the Hα atoms in the alkylidene region (8.0–
20.0 ppm) of any carbene complexes, the only reaction
products are compounds I–III and the tin-containing
olefins. We failed to isolate individual π-complexes I–
III. Therefore, these compounds were identified as
regions of the signals of vinyl protons in the H NMR
spectra of the molybdenum π-complexes.
According to the data of NMR spectroscopy,
compounds I–III exist in solution as isomers differing
by the arrangement of R3Sn groups relative to the ArN
and OR ligands at the molybdenum atom. Keeping at
room temperature for a week did not lead to noticeable
changes in the NMR spectra of π-complexes, indicat-
ing a fairly high thermal stability of the compounds
components of
a
mixture with PhMe2CCH=
1
CHCH2SnR3 by H and 13C NMR spectroscopy using
H–H and C–H correlations. Figures 1–3 show the
17

18
BARINOVA et al.
Isomer 1
Isomer 2
δ, ppm
Fig. 1. 1H NMR spectrum of π-complex I in the region of vinyl protons.
Isomer 2
Isomer 1
δ, ppm
Fig. 2. 1H NMR spectrum of π-complex II in the region of vinyl protons.
formed. The unsaturated derivatives PhMe2CCH=
CHCH2SnR3 (R = Me, Et) were isolated in individual
state in 60–80% yield as colorless oils stable in air.
In accordance with commonly accepted mechanism
for the olefin metathesis [5], at the initial stages of the
reaction the intermediate molybdacyclobutane deriva-
tives containing R3Sn and PhMe2C substituents at the
Ca atom of the metallacycle are formed. Then probably
the β-hydride rearrangement of the molybdacyclo-
butane complex proceeds with the transformation into
an intermediate alkyl hydride compound. In the final
stage a second molecule of the vinylstannane reacts
with the alkyl hydride compound, leading finally to the
1
Their structures were determined by IR, H, 13C NMR
spectroscopy and elemental analysis.
The formation of the tin-containing molybdenum π-
complexes and asymmetric olefin derivatives is
probably a result of the following successive trans-
formations (see the scheme bellow).
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 82 No. 1 2012

MOLYBDENUM TIN-CONTAINING π-COMPLEXES
19
Pri
Pri
CMe2Ph + CH2=CHSnR3
Pri
Pri
SnR3
CH2
N
N
CH
CH
Mo
Mo
R'O
R'O
R'O
R'O
H
CMe2Ph
Pri
Pri
Pri
Pri
SnR3
CH
N
N
CH
+ CH2=CHSnR3
Mo
Mo
CH SnR3
R'O
R'O
R'O
R'O
−PhMe2CCH=CHCH2SnR3
HC
H
H2C
CMe2Ph
R' = CMe2CF3.
formation of the tin-containing olefin PhMe2CCH=
CHCH2SnR3 and the molybdenum π-complex
(CF3Me2CO)2(N-2,6-Pri2C6H3)Mo(CH2=CH-SnR3).
Similar processes of β-hydride rearrangements of
molybdacyclobutane derivatives and the formation of
π-complexes were observed earlier [6–8].
and leads to the formation of high-molecular weight
poly-norbornenes with a predominant content of cis-
units (see the table). The polymer yield after the
repreci-pitation was 90–94%.
The high initiating ability of the molybdenum π-com-
plexes can be probably attributed to the formation of
carbene complexes in the reaction with cycloolefin, which
are then involved in the stages of the chain growth.
Thus, we synthesized and characterized by NMR
spectroscopy new tin-containing molybdenum π-com-
plexes and asymmetric olefin derivatives. The ob-
tained π-complexes actively initiate the metathesis
While studying the catalytic properties of syn-
thesized π-complexes I–III we found that they are able
to initiate the metathesis polymerization of norbornene
without separation from the olefinic derivatives
PhMe2CCH=CHCH2SnR3. The reaction in benzene
solu-tion is completed at room temperature in 2–3 min
Isomer 1
Isomer 2
δ, ppm
Fig. 3. 1H NMR spectrum of π-complex III in the region of vinyl protons.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 82 No. 1 2012

20
BARINOVA et al.
Ar
N
Ar
N
Ar
N
+
−2R3SnCH=CH2
Mo
Mo
CH SnR3
2
Mo
RO
R′O
R′O
R′O
OR
OR′
H2C
Ar
N
Ar
N
n
Mo
RO
n+1Mo
OR′
OR′
R′O
R = Me, Et, Ph, R' = CMe2CF3.
polymerization of norbornene in solution resulting in
the formation of high-molecular weight polynorbor-
nenes with a predominant content of cis-units.
spectrometer FSM 1201 from the liquid films between
the KBr and CaF2 plates.
Molecular weight distribution of polymers was
determined by gel permeation chromatography (GPC)
on a Knauer chromatograph with a Smartline RID
2300 differential refractometer as a detector, using a
set of two Phenomenex columns with the Phenogel
sorbent, pore size of 104 and 105 Å (eluent THF,
2 ml min–1, 40°C). Columns were calibrated with
13 polystyrene standards. Ratio of cis- and trans-units
in the polynorbornene was determined by 13C NMR
spectroscopy using the known technique [11].
EXPERIMENTAL
All operations were carried out in evacuated glass
ampules using standard Schlenk technique. The
solvents used were thoroughly purified and degassed.
PhMe2CCH=Mo(N-2,6-Pri2C6H3](OCMe2CF3)2
and
R3SnCH=CH2 (R=Me, Et, Ph) were synthesized as
described in the literature [9, 10]. Norbornene
(Aldrich) was used without further purification.
(2,6-Diisopropylphenylimido)bis(1,1-dimethyl-
2,2,2-trifluoroethanolato)(trimethylvinylstannane)
molybdenum (I). To a solution of 0.1 g (0.15 mmol) of
PhMe2CC(H)=Mo(N-2,6-Pri2C6H3)(OCMe2CF3)2 in 1.5 ml
NMR spectra of π-complexes I–III and the olefin
derivatives PhMe2CCH=CHCH2SnR3 were obtained
on a Bruker Avance III-400 spectrometer (1H NMR
400 MHz, 13C NMR 100 MHz, 119Sn NMR 149.5 MHz)
in deuterobenzene, the assignment of signals was
carried out using gradient 2D-spectroscopy: proton-
proton correlation (GE-COSY) and proton-carbon
correlation (GE-HSQC). The NMR spectra of polymer
samples in deuterochloroform were obtained on a
Bruker DPX-200 spectrometer (1H NMR 200 MHz,
13C NMR 50 MHz). Chemical shifts are given in ppm
relative to tetramethylsilane as internal reference.
of deuterobenzene 0.06
g
(0.3 mmol) of
Me3SnCH=CH2 in 1 ml of C6D6 was added. According
1
to the data of H NMR spectroscopy the reaction
completed within 5 min at room temperature. The
solvent was removed by evaporation in vacuum. The
dark-red oily residue was a mixture of I and 2-methyl-
2-phenyl-5-(trimethylstannyl)pent-3-ene. The overall
yield of compounds was 0.12 g (80%). The resulting π-
complex (Me3SnCH=CH2)Mo(N-2,6-Pri2C6H3)·
(OCMe2CF3)2, according to the data of NMR
spectroscopy, was a mixture of two isomers with a
The IR spectra of compounds PhMe2CCH=
CHCH2SnR3 (R = Et, Me) were recorded on a FTIR
1
ratio of 62:38%. Isomer 1, 62%. H NMR spectrum
(C6D6, δ, ppm, J, Hz): 6.97 br.s (3H, Harom), 3.82 sept
Characteristics of the synthesized polynorbornenes (the ratio
of monomer: initiator = 50:1)
3
(2H, CHMe2, JHH 6.8), 2.67 m (2H, CH2=CHSnMe3,
3
3
2JHH 3.5, JHH 14.5), 2.06 t (1H, CH2=CHSnMe3, JHH
14.5), 1.36 and 1.32 s (6H each, OCMe2CF3), 1.26 d
(12H, CHMe2), 0.07 s [9H, Sn(CH3)3]. 13C NMR
spectrum (C6D6, δ, ppm, J, Hz): 149.6 (Cipso), 145.5
Initiator
trans:cis
MW
MN
MW/MN
29:71
23:77
27:73
286363
1107500
1390000
225340
557700
955000
1.27
1.98
1.46
I
II
III
1
(Co), 128.0 (Cp) 126.2 q (OCMe2CF3, JCF 276.0),
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 82 No. 1 2012

MOLYBDENUM TIN-CONTAINING π-COMPLEXES
21
2
124.9 (Cm) 79.8 q (OCMe2CF3, JCF 28.9), 58.9
(CH2=CHSnMe3), 56.7 (CH2=CHSnMe3), 29.2 and
28.8 (CHMe2), 28.5 (CHMe2), 23.98 and 22.9
(2,6-diisopropylphenylimido)bis(1,1-di-methyl-2,2,2-
triftoretanolato)(trimethylvinylstannane)molybdenum
II and 2-methyl-2-phenyl-5-(triethyl-stannyl)pent-3-
ene. The overall yield of compounds was 0.17 g
(94%). The resulting π-complex (Et3SnCH=CH2)Mo·
(N-2,6-Pri2C6H3)(OCMe2CF3)2 was a mixture of two
1
(OCMe2CF3), –7.89 (SnCH3). Isomer 2 (38%), H
NMR spectrum (C6D6, δ, ppm, J, Hz): 6.97 br.s (3H,
3
H
arom), 3.82 sept (2H, CHMe2, JHH 6.8), 3.62 d (1H,
CH2=CHSnMe3, 3JHH 12.05), 2.43
d
(1H,
isomers with a ratio of 74:26%. Isomer 1 (74%). H
1
CH2=CHSnMe3, 3JHH 12.05), 1.36 and 1.32 s (6H each,
NMR spectrum (δ, ppm, J, Hz): 6.97 br.s (3H, Harom),
2
3
OCMe2CF3), 1.26 d (12H, CHMe2, JHH 6.8), 0.07 s
3.85 sept (2H, CHMe2, JHH 6.8), 2.70 m (2H,
[9H, Sn(CH3)3]. 13C NMR spectrum (C6D6, δ, ppm, J,
CH2=CHSnEt3 JHH 14.5), 2.05 t (1H, CH2=CHSnEt3,
3
Hz): 149.6 (Cipso), 145.5 (Co), 128.0 (Cp) 126.2 q
3JHH 14.5), 1.38 and 1.35 s (6H each, OCMe2CF3),
1
2
(OCMe2CF3 JCF 276.0), 124.9 (Cm), 79.8 q (OCMe2F3,
1.24 d (12H, CHMe2, JHH 6.5), 1.17 t (9H,
2JCF 28.9), 73.8 (CH2=CHSnMe3), 68.9
(CH2=CHSnMe3), 29.2 and 28.8 ( CHMe2), 28.5
(CHMe2), 23.98 and 22.9 (OCMe2CF3), –7.89 (SnCH3).
SnCH2CH3, JHH 7.9), 0.85 q (6H, SnCH2CH3, JHH
7.8). 13C NMR spectrum (C6D6, δ, ppm, J, Hz): 150.0
(Cipso), 145.8 (Co), 128.0 (Cp) 127.5 q (OCMe2CF3,
1JCF 286.0), 123.3 (Cm), 79.3 q (OCMe2CF3, 2JCF 28.5),
58.0 (CH2=CHSnEt3), 57.9 (CH2=CHSnEt3), 29.9 and
29.5 (CHMe2) , 28.6 (CHMe2), 24.1 and 23.3 (OCMe2
CF3), 2.4 (SnCH2CH3), 1.02 (SnCH2CH3). 119Sn NMR
2
2
2-Methyl-2-phenyl-5-(trimethylstannyl)pent-3-ene.
After fractionation of the reaction mixture in vacuum
(10–2 mm Hg) at 100–110°C the olefin derivative
PhMe2CCH=CHCH2SnMe3 was isolated as air stable
colorless oil. Yield 0.05 g (62%). IR spectrum, ν, cm–1:
3083 w, 3060 w (Carom–H), 2966 s, 2914 s, 2869 m
1
spectrum (C6D6, δ, ppm): 36.2. Isomer 2 (26%), H
NMR spectrum (C6D6, δ, ppm, J, Hz): 6.97 br.s (3H,
3
H
arom), 3.85 sept (2H, CHMe2 JHH 6.8), 3.26 d.d (1H,
(C–H, CH3), 1646 w (C=C), 1600 w, 1492 m (Carom
arom, Ph), 1462 m (C–H, CH3), 1446 m (CH, CH2Sn),
–
2
3
CH2=CHSnEt3 JHH 2.2, JHH 14.0), 3.11 t (1H,
C
CH2=CHSnEt3, 3JHH 14.0), 2.39 d.d (1H,
1383 w (C–H, CH3), 1186 w (C–H, CH3), 1100 m,
1030 m (CH, SnMe3), 698 m, 763 m (Carom–H), 527 m,
512 [Sn–C, Sn(CH3)3]. Signals in the 1H and 13C NMR
spectra of the isolated compounds correspond to the
signals of PhMe2CCH=CHCH2SnMe3 in the reaction
2
3
CH2=CHSnEt2 JHH 2.5, JHH 14.0), 1.38 and 1.35 s
2
(6H each, OCMe2CF3), 1.24 d (12H, CHMe2, JHH
2
6.5), 1.17 t (9H, SnCH2CH3, JHH 7.9), 0.85 q (6H,
SnCH2CH3, JHH 7.8). 13C NMR spectrum (C6D6, δ,
2
ppm, J, Hz): 150.0 (Cipso), 145.8 (Co), 128.0 (Cp),
1
mixture prior to frac-tionation. H NMR spectrum
1
127.5 q (OCMe2CF3, JCF 286.0), 123.3 (Cm), 79.3 q
2
(C6D6, δ, ppm, J, Hz): 7.35 d (2H, Harom, JHH 7.8),
2
(OCMe2CF3, JCF 28.5), 70.6 (CH2=CHSnEt3), 66.0
7.30 t (2H, Harom, 2JHH 7.4), 7.18 t (1H, Harom, 2JHH 7.2),
5.48 m (2H, CH=CH, 2JHH 7.8, 3JHH 15.4), 1.76 d (2H,
CH2Sn, JHSn 64.4), 1.38 s (6H, CMe2Ph), 0.09 s (9H,
SnCH3, JHSn 51.9). 13C NMR spectrum (C6D6, δ, ppm):
149.91 (Cipso, Ph), 136.03 (CH=CH), 127.92 (Cm, Ph),
126.23 (Co, Ph), 125.48 (Cp, Ph), 125.06 (CH=CH),
40.35 (CMe2Ph), 29.34 (CMe2Ph), 16.11 (CH2Sn),
–10.13 (SnCH3). 119Sn NMR spectrum (C6D6, δ, ppm):
–2.9. Found, %: C 56.19, H 7.71. C15H24Sn.
Calculated, %: C 55.8, H 7.44.
(CH2=CHSnEt3), 29.9 and 29.5 (CHMe2), 28.6
(CHMe2), 24.11 and 23.3 (OCMe2CF3), 2.41
(SnCH2CH3), 1.02 (SnCH2CH3). 119Sn NMR spectrum
(C6D6, δ, ppm): 91.1.
2-Methyl-2-phenyl-5-(triethylstannyl)pent-3-ene.
The olefin derivative PhMe2CCH=CHCH2SnEt3 was
isolated by fractionation of the reaction mixture in a
vacuum (10–2 mm Hg) at 100–110°C as air stable,
colorless oil. Yield 0.04 g (80%). IR spectrum (ν, cm–1:
3083 w, 3060 w, 3022 w (Carom–H), 2955 m, 2943 s,
2900 s, 2865 (C–H, CH3, CH2), 1645 w (C=C), 1600
w, 1490 w (Carom–Carom, Ph), 1460 m, 1420 m (C–H,
CH3, CH2), 1380 w, 1360 w (C–H, CH3), 1258 w
(C–H, CH3, C(CH3)2Ph), 1232 w, 1186 w (C–H, CH3),
1096 m, 1017 m. (Carom–H, Ph), 969 m, 807 m
(HC=CH), 761 m (Carom–H), 742 (C–H, CH2–Sn) 506
(2,6-Diisopropylphenylimido)bis(1,1-dimethyl-2,2,2-
trifluoroethanolato)(triethylvinylstannane)molyb-
denum (II). To a solution of PhMe2CC(H)=Mo(N-2,6-
Pri2C6H3)(OCMe2CF3)2 0.11 g (0.16 mmol) in 1.5 ml of
deuterobenzene 0.07 g (0.3 mmol) of Et3SnCH=CH2
1
was added at room temperature. According to the H
NMR spectroscopy, the reaction was completed at
room temperature within 5 min. The solvent was
removed by evaporation in vacuum at room tem-
perature. The red-brown oily residue was a mixture of
m (Sn–C, SnEt3). 1H NMR spectrum (C6D6, δ, ppm, J,
2
Hz): 7.38 d (2H, Harom, JHH 7.5), 7.24 t (2H, Harom
,
2JHH 7.2), 7.14 t (1H, Harom, JHH 6.9), 5.57 m (2H,
2
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 82 No. 1 2012

22
BARINOVA et al.
CH=CH), 1.80 d [2H, CH2Sn, J(H–119Sn) 57.8], 1.39 s
(6.38 mmol) of norbornene in 1 ml of benzene was
charged at room temperature. After 3 min the reaction
mixture became viscous. The resulting polymer was
dissolved in THF and benzaldehyde was added for the
decomposition of the catalyst. Then polymer pre-
cipitated with methanol, purified by reprecipitation
three times with methanol from THF and dried in
vacuum at room temperature until the weight was un-
changed. The polymer yield 0.57 g (96%). Experi-
ments on the polymerization of norbornene with the
initiators II and III were carried our similarly.
2
(6H, CMe2Ph), 1.20 m (9H, SnCH2CH3, JHH 7.6.),
2
0.86 q (6H, SnCH2CH3, JHH 8.0). 13C NMR spectrum
(C6D6, δ, ppm): 149.71 (Cipso), 136.02 (CH=CH), 128.0
(Cm), 126.3 (Co), 125.6 (Cp) 125.4 (CH=CH), 40.2
(CMe2Ph), 29.2 (CMe2Ph), 13.02 (CH2Sn), 10.9
(SnCH2CH3), 0.37 (SnCH2CH3). 119Sn NMR spectrum
(C6D6, δ, ppm): –4.9. Found, %: C 59.42, H 8.29.
C18H30Sn. Calculated, %: C 59.23, H 8.23.
(2,6-Diisopropylphenylimido)bis(1,1-dimethyl-2,2,2-
trifluoroethanolato)(triphenylvinylstannane)molyb-
denum (III). To a solution of 0.14 g (0.21 mmol) of
PhMe2CC(H)=Mo(N-2,6-Pri2C6H3)(OCMe2CF3)2 in
1.5 ml of deuterobenzene a solution of 0.12 g
(0.31 mmol) of Ph3SnCH=CH2 in 1 ml of C6D6 was
added at room temperature. According to the 1H NMR
spectroscopy the reaction at room temperature com-
pleted within 10 min. The solvent was removed by
evaporation in vacuum at room temperature. The red-
brown oily residue was a mixture of (2,6-diiso-
propylphenylimido)bis(1,1-dimethyl-2,2,2-trifluoro-
etanolato)(triphenylvinylstannane)molybdenum (III) and
2-methyl-2-phenyl-5-(triphenylstannyl)pent-3-ene. The
overall yield 0.26 g (96%). NMR study showed that π-com-
plex (Ph3SnCH=CH2)Mo(N-2,6-Pri2C6H3)(OCMe2CF3)2
in C6D6 consisted of two isomers with a ratio of 50:
ACKNOWLEDGMENTS
This work was supported by the Russian Founda-
tion for Basic Research (project no. 08-03-00436).
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1
50%. Isomer 1. H NMR spectrum (C6D6, δ, ppm, J,
Hz): 7.23–6.90 m (15H, SnPh3), 7.03 br.s [3H, 2,6-
3
(Pr-i)2C6H3], 3.99 sept (2H, CHMe2, JHH 6.8), 3.56 m
(1H, CH2=CHSnPh3), 2.78 d (1H, CH2=CHSnPh3),
2.60 d (1H, CH2=CHSnPh3), 1.38 and 1.35 s (6H each,
2
OCMe2CF3), 1.25 d (12H, CHMe2, JHH 6.5). 13C
NMR spectrum (C6D6, δ, ppm): 152.8, 145.2, 136.8,
137.2, 128.9, 128.4 (Carom), 127.5 (OCMe2CF3), 122.6
(Carom), 79.8 (OCMe2CF3), 57.6 (CH2=CHSnPh3), 54.9
(CH2= CHSnPh3), 29.9 and 29.5 (CHMe2), 28.6
5. Chauvin, Y., Angew. Chem. Int. Ed., 2006, vol. 45,
p. 3741.
1
6. Robbins, J., Bazan, G.C., Murdzek, J.S., O’Regan, M.B.,
and Schrock, R.R., Organometallics, 1991, vol. 10,
p. 2902.
7. Tsang, W.C.P., Jamieson, J.Y., Aeilts, S.L., Hultzsch, K.C.,
Schrock, R.R., and Hoveyda, A.H., Organometallics,
2004, vol. 23, p. 1997.
8. Schrock, R.R., Duval-Lungulescu, M., Tsang, W.C.P.,
and Hoveyda, A.H., J. Am. Chem. Soc., 2004, vol. 126,
p. 1948.
9. Oskam, J.H., Fox, H.H., Yap, K.B., McConvill, D.H.,
O’Dell, R., Lishtenstein, B.J., and Schrock, R.R.,
J. Organomet. Chem., 1993, vol. 459, p. 185.
(CHMe2), 24.1 and 23.3 (OCMe2CF3). Isomer 2. H
NMR spectrum (C6D6, δ, ppm, J, Hz): 6.90–7.23m
(15H, SnPh3), 7.03 br.s [3H, 2,6-(Pr-i)2C6H3], 3.99 sept
3
(2H, CHMe2, JHH 6.8), 3.88 d (1H, CH2=CHSnPh3,
3
3JHH 12.04), 3.08 d (2H, CH2=CHSnPh3, JHH 12.04),
1.38 and 1.35 s (6H each, OCMe2CF3), 1.25 d (12H,
CHMe2, 2JHH 6.5). 13C NMR spectrum (C6D6, δ, ppm):
152.8, 145.2, 136.8, 137.2, 128.9, 128.4 (Carom) 126.2
q (OCMe2CF3), 122.6 (Carom), 79.8 (OCMe2CF3), 79.6
(CH2=CHSnPh3), 68.2 (CH2=CHSnPh3), 29.9 and 28.8
(CHMe2), 28.6 (CHMe2), 24.1 and 23.3 (OCMe2CF3).
The norbornene metathesis polymerization. Into
an ampule containing 0.03 g (0.04 mmol) of π-
10. Rosenberg, S.D., Walburn, J.J., Stankovich, T.P.,
Balint, A.E., and Ramdsen, H.E., J. Org. Chem., 1957,
vol. 22, p. 8200.
complex
I
(equimolar mixture with PhMe2C–
CH=CHCH2SnMe3) in 1 ml of benzene 0.60 g
11. Hamilton, J.G., Polymer, 1998, vol. 37, no. 8, p. 1669.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 82 No. 1 2012