S. Go´mez-Ruiz et al. / Journal of Organometallic Chemistry 693 (2008) 601–610
609
123.2, 131.0, 133.1, 136.7 (C5Ph4), 126.5, 127.4, 128.6,
References
130.8, 133.5, 143.0, 145.2, 145.5 (Ph). MS electron impact
(m/e (relative intensity)): 709 (67) [M+], 673 (8) [M+ꢀCl],
617 (49) [M+ꢀClꢀBut], 587 (55) [M+ꢀClꢀButꢀ2ꢁMe].
Anal. Calc. for C40H38Cl2SiZr: C, 67.77; H, 5.40. Found:
C, 67.30; H, 5.31%.
[1] (a) N.J. Long, Metallocenes. An Introduction to Sandwich Com-
plexes, Blackwell Science Ltd., Oxford, 1998;
(b) A. Togni, Metallocenes, Wiley–VCH, Weinheim, 1998.
[2] (a) M.P. Castellani, J.M. Wright, S.J. Geib, A.L. Rheingold, W.C.
Trogler, Organometallics 5 (1986) 1116;
(b) F.O. Arp, G.C. Fu, J. Am. Chem. Soc. 128 (2006) 14264;
(c) R. Peters, Z.-Q. Xin, D.F. Fischer, W.B. Schweizer, Organome-
tallics 25 (2006) 2917;
4.10. Polymerization of ethylene
(d) H. Schumann, K. Suehring, Z. Naturforsch B 60 (2005) 383;
(e) I.D. Hills, G.C. Fu, Angew. Chem., Int. Ed. 42 (2003) 3921;
(f) A.H. Mermerian, G.C. Fu, J. Am. Chem. Soc. 125 (2003) 4050;
(g) J. Norinder, H.K. Cotton, J.-E. Baeckvall, J. Org. Chem. 67
(2002) 9096.
The zirconocene catalyst (6 lmol), MAO (10% in tolu-
ene) (6000 lmol) and toluene (200 mL) were mixed
together for 15 min in a 1 l glass autoclave. The N2 pressure
inside the autoclave was reduced by applying vacuum. Eth-
ylene pressure of 2 bar was then applied and maintained to
the autoclave and stirring of the mixture commenced
(1000 rpm). After exactly 15 min, stirring was halted and
the ethylene pressure released. Excess MAO was then
destroyed by adding cautiously a mixture of methanol/
HCl (90:10). The polymer was isolated by filtration and
washed with ethanol and dried under vacuum at 90 °C
for 16 h.
[3] M.P. Castellani, S.J. Geib, A.L. Rheingold, W.C. Trogler, Organo-
metallics 6 (1987) 1703.
[4] M.P. Castellani, S.J. Geib, A.L. Rheingold, W.C. Trogler, Organo-
metallics 6 (1987) 2524.
[5] (a) U. Thewaldt, G. Schmidt, J. Organomet. Chem. 412 (1991) 343;
(b) B. Rieger, T. Repo, G. Jany, Polymer Bull. 35 (1995) 87;
(c) B. Rieger, M. Steinmann, R. Fawzi, Chem. Ber. 125 (1992) 2373;
(d) D.L. Greene, A. Chau, M. Monreal, C. Mendez, I. Cruz, T. Wenj,
W. Tikkanen, B. Schick, K. Kantardjieff, J. Organomet. Chem. 682
(2003) 8;
(e) J. An, L. Urrieta, R. Williams, W. Tikkanen, R. Bau, M. Yousufud-
din, J. Organomet. Chem. 690 (2005) 4376;
4.11. Theoretical calculations
(f) D.L. Green, O.A. Villalta, D.M. Macias, A. Gonzalez, W. Tikkanen,
B. Schick, K. Kantardjieff, Inorg. Chem. Commun. 2 (1999) 311;
(g) S.-S. Xu, F. Yuan, S.-S. He, B.-Q. Wang, X.-Z. Zhou, F.-L. Zou, Y.
Li, Youji Huaxue 23 (2003) 187;
(h) A. Altomare, F. Ciardelli, N. Tirelli, R. Solaro, Macromolecules 30
(1997) 1298;
(i)F. Ciardelli,A. Altomare,G. Arribas,G. Conti,F. Masi, F. Menconi,
Stud. Surf. Sci. Catal. 89 (1994) 257;
(j) G. Conti, G. Arribas, A. Altomare, B. Mendez, F. Ciardelli, Z.
Naturforsch., B: Chem. Sci. 50 (1995) 411;
(k) D.W. Stephan, J.C. Stewart, F. Guerin, S. Courtenay, J. Kickham,
E. Hollink, C. Beddie, A. Hoskin, T. Graham, P. Wei, R.E. Spence, W.
Xu, L. Koch, X. Gao, D.G. Harrison, Organometallics 22 (2003) 1937;
(l) S. Barry, A. Kucht, H. Kucht, M.D. Rausch, J. Organomet. Chem.
489 (1995) 195;
The Becke 1988 [18] for exchange and Perdew 1986 [19]
for correlation gradient corrected functional were used for
all the geometry optimization calculations. We selected a
double zeta quality numerical basis set which included
polarization (DZP) for all atoms including hydrogen atoms
[20]. For the Zr metal atom a pseudopotential [21] was
used. All the calculations were carried out with the DMOL
[20,22] package included in the MATERIALSSTUDIO [23]
software.
Acknowledgements
(m) A. Kucht, H. Kucht, S. Barry, J.C.W. Chien, M.D. Rausch,
Organometallics 12 (1993) 3075;
(n) K.H. Thiele, F. Rehbaum, H. Baumann, H. Schumann, F.H.
Goerlitz, R. Weimann, Z. Anorg. Allgem. Chem. 613 (1992) 76.
[6] See for example: (a) L. Resconi, L. Cavallo, A. Fait, F. Piemontesi,
Chem. Rev. 100 (2000) 1253;
We gratefully acknowledge financial support from the
´
Ministerio de Educacion y Ciencia, Spain (Grants numbers
CTQ2005-07918-C02-02/BQU and MAT2006-400), the
Comunidad de Madrid (S-0505/PPQ-0328), the Universi-
dad Rey Juan Carlos (graduate fellowship for D.
(b) H.H. Brintzinger, D. Fischer, R. Mulhaupt, B. Rieger, R.M.
¨
Waymouth, Angew. Chem., Int. Ed. Engl. 36 (1995) 1143;
(c) J. Zhang, X. Wang, G.-X. Jin, Coord. Chem. Rev. 250 (2006) 95;
(d) S. Prashar, A. Antinolo, A. Otero, Coord. Chem. Rev. 250 (2006)
˜
´
Polo-Ceron) and the Alexander von Humboldt-Stiftung
´
(Humboldt-Fellowship for S. Gomez-Ruiz). J. Ramos
thanks CSIC for financial support through an I3P tenure
track.
133;
(e) B. Wang, Coord. Chem. Rev. 250 (2006) 242;
(f) P.C. Mo¨hring, N.J. Coville, Coord. Chem. Rev. 250 (2006) 18.
´
[7] (a) A. Antinolo, I. Lopez-Solera, I. Orive, A. Otero, S. Prashar,
˜
Appendix A. Supplementary material
´
A.M. Rodrıguez, E. Villasenor, Organometallics 20 (2001) 71;
˜
´
(b) A. Antinolo, I. Lopez-Solera, A. Otero, S. Prashar, A.M.
˜
CCDC 658048 and 658049 contain the supplementary
crystallographic data for this paper. These data can be
obtained free of charge from The Cambridge Crystallo-
quest/cif. PDB files of the calculated structures are
provided as supplementary material. Supplementary data
associated with this article can be found, in the online ver-
´
Rodrıguez, E. Villasenor, Organometallics 21 (2002) 2460;
(c) A. Antinolo, M. Fajardo, S. Go´mez-Ruiz, I. Lo´pez-Solera, A.
Otero, S. Prashar, A.M. Rodrıguez, J. Organomet. Chem. 683 (2003)
˜
˜
´
11;
´
´
(d) A. Antinolo, M. Fajardo, S. Gomez-Ruiz, I. Lopez-Solera, A.
˜
Otero, S. Prashar, Organometallics 23 (2004) 4062;
(e) S. Gomez-Ruiz, S. Prashar, M. Fajardo, A. Antinolo, A. Otero,
˜
M.A. Maestro, V. Volkis, M.S. Eisen, C.J. Pastor, Polyhedron 24
(2005) 1298;
´