F. Simal et al. / Journal of Organometallic Chemistry 558 (1998) 163–170
169
were based on the diazocompound and calculated with
dibutyl fumarate or diethyl phtalate as internal
standards.
5
.3. Polymerization reactions
Scheme 5.
The reaction were carried out in chlorobenzene (cata-
nium complexes were prepared according to literature
lyst 0.0075 mmol, diazo compound 0.1 mmol) and the
polymers (polynorbornenes) isolated and identified
along the lines reported in ref. [11] and [41].
[
33–36]. Products were identified by comparison of
their retention times with authentic samples on two
different GC capillary columns and by coupled GC-
MS. GC analysis were performed on a 30 m ×0.32
mm WCOT FFAP-CB column and a 30 m ×0.53
CP-Sil8-CB column, with FID and nitrogen as carrier
gas.
Acknowledgements
We thank the European Union for finantial support
(
Grant INTAS 94-393 and Human Capital and Mobil-
ity Contract ERBCHRX93 0147).
5.2. Cyclopropanation and homologation reactions
In a typical experiment, the catalyst (0.005 mmol)
and the olefin (20 mmol) were put into a round-bot-
tomed flask and heated to the reaction temperature
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usually 60 or 100°C) under nitrogen. One ml of a
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−
1
solution of the diazoester in the olefin (1 mol l ) was
then added dropwise over 4 h to the vigorously stirred
system via a syringe pump. When necessary, heating
was continued for a few more hours, especially with the
less active catalysts (see text). The reaction products
were then analyzed by gas chromatography. The yields
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[
[
[
[
1
2
1
2
2
1
2
2
6
7
7
8
8
9
1
a
a
c
c
c
d
d
d
N CHSi(CH )
B0.5
B0.5
B0.5
54
—
—
—
—
—
—
2
3 3
(
N CHSi(CH )
2
3 3
N CHSi(CH )
2
3 3
N CHSi(CH )
0.75 21 000
2
3 3
N CHCO C H
4
0.82
0.74
0.72 19 000
7000
2
2
2
5
N CHSi(CH )
B0.5
50
—
2
3 3
N CHSi(CH )
2
3 3
N CHCO C H
3
0.66
—
0.45 34 000
0.58 22 000
0.73 22 000
—
—
2
2 2
5
N CHSi(CH )
B0.5
47
23
2
3 3
[
14] A. Demonceau, E. Abreu Dias, C.A. Lemoine, A.W. Stumpf,
A.F. Noels, C. Pietraszuk, J. Gulinski, B. Marciniec, Tetrahe-
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N CHSi(CH )
2
3 3
N CHCO C H
2
2
2
5
N CHSi(CH )
39
2
3 3
[
[
[
[
[
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N CHCO C H
B0.5
7
19
0.80
0.87
0.71
—
—
—
2
2 2
5
8
81.
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N CHSi(CH )
2
3 3
0
N CHSi(CH )
2
3 3
(
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a
Reaction conditions: 0.015 mmol of catalyst and 0.5 g of norbor-
nene were dissolved under nitrogen in 30 ml of purified chloroben-
zene. The resulting solution was heated to 60°C over 20 min. 0.1
mmol of diazo compound diluted in 1 ml of chlorobenzene was then
added to the reaction mixture via a syringe over 0.5 h. The reaction
mixture was kept at 60°C for 5 h, then cooled to room temperature,
and precipitated in 700 ml of technical methanol.
Fraction of cis units, determined by 1H- and 13C-NMR.
Determined by GPC, using polystyrene standards.
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b
c