218
E. Polo et al. / Journal of Organometallic Chemistry 577 (1999) 211–218
Anal. Found: C, 56.8; H, 6.6; Cl, 16.2. C H Cl Zr
428.55) Calc.: C, 56.1; H, 6.1; Cl, 16.6%. H-NMR
References
20
1
26
2
(
(
(
(
[
1] (a) J.A. Ewen, J. Am. Chem. Soc. 106 (1984) 6355. (b) J.A.
Ewen, in: T. Keii, K. Soga (Eds.), Catalytic Polymerization of
Olefins, Elsevier, Tokyo, 1986, p. 271. (c) J.A. Ewen, H.
Zhang, L. Haspeslagh, J.L. Atwood, J. Am. Chem. Soc. 109
CDCl ): l 1.50–1.80 (m, 8H), 2.15 (s, 6H), 2.50–2.70
3
13
m, 4H), 2.70–2.90 (m, 4H), 6.90 (s, 4H) ppm; C-NMR
CDCl ): l 16.2, 22.5, 24.7, 114.6, 129.4, 139.5 ppm.
3
(
1987) 6544. (d) W. Kaminsky, Angew. Makromol. Chem. 145
3
.13. Ethylene-bis(10-methyl bicyclo [5:3:0] dec-7,9
(1987) 149. (e) W. Kaminsky, in: T. Keii, K. Soga (Eds.),
Catalytic Polymerization of Olefins, Elsevier, Tokyo, 1986, p.
diene) 14
2
4
93. (f) F.P.C. Morhing, N.J. Coville, J. Organomet. Chem.
79 (1994) 1. (g) F.R.W.P. Wild, M. Wasiucionek, G. Huttner,
A solution of 1,2 dibromoethane (181 ml, 2.1 mmol,
H.H. Brintzinger, J. Organomet. Chem. 288 (1985) 63. (h) F.
Wochner, L. Zsolnai, G. Huttner, H.H. Brintzinger, J.
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Huttner, H.H. Brintzinger, J. Organomet. Chem. 322 (1987)
dried over anhydrous CaCl ) dissolved in THF and
cooled to 0°C, was slowly added via a thin cannula to
a solution of the organolithium compound 12 (600 mg,
4
2
6
5. (j) A. Sch a¨ fer, E. Karl, F.R.W.P. Wild, L. Zsolnai, G.
Huttner, H.H. Brintzinger, J. Organomet. Chem. 328 (1987)
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Brintzinger, J. Organomet. Chem. 369 (1989) 343.
.3 mmol) dissolved in 20 ml of THF and cooled to
78°C. The resulting pale yellow solution was allowed
−
8
to warm to r.t. and stirred for 24 h. Saturated ammo-
nium chloride solution was added to quench the reac-
tion. Extraction with diethyl ether, drying and
evaporation gave 543 mg of the bis-diene 14 (yield: 85%)
which was used in the following reaction without further
purification.
[2] J.C.W. Chien, D. He, J. Polym. Sci Part A: Polym. Chem. 29
(1991) 585.
3] Typical examples: (a) F.R.W.P. Wild, L. Zsolnai, G. Huttner,
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A.L. Rheingold, N.P. Robinson, J. Whelan, B. Bosnich,
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[
[
4] (a) P.C. Wailes, R.S.P. Coutts, H. Weigold, Organometallic
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5
3
.14. Ethylene-bis(p -10-methyl bicyclo [5:3:0] dec-7,9
dienyl) zirconium bis(dimethyl amide) 15
The bis-diene 14 (0.543 g, 1.83 mmol) was dissolved
in toluene and added to a suspension of zirconium
tetrakis(dimethylamide) (505 mg, 1.87 mmol) in toluene.
The resulting cloudy solution was refluxed for 18 h,
allowed to cool, and filtered. A total of 0.365 g of a
[
(
d) R.N. Austin, T.J. Clark, T.E. Dickson, C.M. Killian, T.A.
Nile, D.J. Schabacher, A.T. McPhail, J. Organomet. Chem.
91(1995) 11. (e) W.T. Scroggins, M.F. Rettig, R.M. Wing,
cream coloured solid were obtained (unoptimised yield:
2%). An aliquot was removed and analysed by H-
1
4
4
NMR analysis which showed only the peaks correspond-
ing to the rac-isomer of 15.
Inorg. Chem. 15 (1976) 1381. (f) W.A. Herrmann, R. Anwan-
der, H. Riepl, W. Scherer, C.R. Whitaker, Organometallics 12
(
1993) 4342. (g) R.L. Halterman, T.M. Ramsey, Organometal-
lics 12 (1993) 2879. (h) P.L. Pauson, Tetrahedron 41(1985)
855. (i) G. Erker, C. Psiorz, R.Z. Fr o¨ lich, Naturforsch 50b
(1995) 469.
Anal. Found: C, 67.0; H, 8.9; N, 5.7. C H N Zr
2
6
40
2
1
(
471.83) Calc.: C, 66.2; H, 8.5; N, 5.9%. H-NMR
5
(
CDCl ): l 1.72–1.78 (m, 4H), 2.12 (s, 6H), 2.30–2.35
3
(
5
2
m, 8H), 2.50 (s, 12H), 2.71 (s, 4H), 2.80–2.85 (m, 4H),
[6] A.P. Krapcho, J. Diamanti, C. Cayen, R. Bingham, Org.
Synth. 47 (1966) 20.
1
3
.90 (s, 2H) ppm; C-NMR (CDCl ): l 16.1, 23.1, 23.4,
3
[
[
[
7] A. Barco, S. Benetti, G.P. Pollini, Synthesis (1973) 316.
8] A.M. Islam, R.A. Raphael, J. Chem. Soc. (1952) 4086.
9] (a) W.A. Herrmann, J. Rohrmann, E. Herdtweck, W. Spalek,
A. Winter, Angew. Chem. Int. Ed. Engl. 28 (1989) 1536. (b)
W. Spalek, M. Antberg, J. Rohrmann, A. Winter, B. Bach-
mann, P. Kiprof, J. Behm, W.A. Herrmann, Angew. Chem.
Int. Ed Engl. 31 (1992) 1347. (c) T. Mise, S. Miya, H. Ya-
mazaki, Chem. Lett. 104 (1989) 1853. (d) W. R o¨ ll, H.H.
Brintzinger, B. Rieger, R. Zolk, Angew. Chem. Int. Ed. Engl.
4.4, 25.2, 28.7, 46.8, 126.8, 128.2, 129.2, 131.4, 139.9
ppm.
Acknowledgements
We thank A. Barco and S. Benetti (University of
Ferrara) for helpful advice with the organic syntheses.
CNR Short Term Fellowship Program, years 1995/96
and 1996/97 for Eleonora Polo’s stages in Oxford.
2
9 (1990) 279.
[
10] G.M. Diamond, S. Rodewald, R.F. Jordan, Organometallics
14 (1995) 5.
.