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Article

From Unstable to Stable: Half-Metallocene Catalysts for Olefin Polymerization^†

Supporting Info

Prabhuodeyara M. Gurubasavaraj, Herbert W. Roesky*, Bijan Nekoueishahraki, Aritra Pal and Regine Herbst-Irmer

Institute of Inorganic Chemistry, University of Göttingen, Tammannstrasse 4, 37077 Göttingen, Germany

Inorg. Chem., 2008, 47 (12), pp 5324–5331

DOI: 10.1021/ic800198e

Publication Date (Web): May 21, 2008

†

Dedicated to Professor George M. Sheldrick on the occasion of his 65th birthday.

* To whom correspondence should be addressed. E-mail: hroesky@gwdg.de.

Abstract

The reaction of LAlMeOH [L = CH(N(Ar)(CMe))₂, Ar = 2,6-i-Pr₂C₆H₃] with CpTiMe₃, Cp*TiMe₃, and Cp*ZrMe₃ was investigated to yield LAlMe(μ-O)TiMe₂Cp (2), LAlMe(μ-O)TiMe₂Cp* (3), and LAlMe(μ-O)ZrMe₂Cp* (4), respectively. The resulting compounds 2−4 are stable at elevated temperatures, in contrast to their precursors such as CpTiMe₃ and Cp*ZrMe₃, which already decompose below room temperature. Compounds 2−4 were characterized by single-crystal X-ray structural analysis. Compounds 2 and 3 were tested for ethylene polymerization in the presence of methylaluminoxane. The half-metallocene complex 3 has higher activity compared to 2. The polydispersities are in the range from 2.8 to 4.2. A copolymerization with styrene was not observed.