Synthesis of zirconocene amides and ketimides and an investigation into their ethylene polymerization activity

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Henderson, K.W. and Hind, A. and Kennedy, A.R. and McKeown, A.E. and Mulvey, R.E. (2002) Synthesis of zirconocene amides and ketimides and an investigation into their ethylene polymerization activity. Journal of Organometallic Chemistry, 656 (1-2). pp. 63-70. ISSN 0022-328X (http://dx.doi.org/10.1016/S0022-328X(02)01559-0)

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Abstract

The zirconocene amide [Cp2Zr(Cl)N(CH2Ph)(2)] (5), and the zirconbcene ketimides [Cp2Zr(Cl)N=C(Bu')Ph] (7), and [Cp2Zr(Cl)N=C(NMe2)(2)] (9), have been prepared by the transmetallation reactions between the appropriate lithiated organonitrogen compounds and zirconocene dichloride (2). In addition, their methylated derivatives [Cp2Zr(Me)N(CH2Ph)(2)] (6), [Cp2Zr(Me)N=C(Bu')Ph] (8), and [Cp2Zr(Me)N=C(NMe2)(2)] (10), have been prepared by the reaction of each of the complexes 5, 7 and 9 with MeLi. Compounds 5 and 7 have been characterized by X-ray crystallography and the structure of the cocrystalline complex [Cp2Zr(Cl)N=C(Bu)Ph](0.4)[Cp2Zr(Me)N=C(Bu')Ph](0.6) (14), has similarly been determined. All of the complexes 5-10 are active catalysts for the polymerization of ethylene in the presence of a MAO cocatalyst. In contrast, no polymer was produced using B(C6F5)(3) as an activator, indicating that direct alkene insertion into the Zr-N bonds does not occur.

ORCID iDs

Henderson, K.W., Hind, A., Kennedy, A.R. ORCID logoORCID: https://orcid.org/0000-0003-3652-6015, McKeown, A.E. and Mulvey, R.E. ORCID logoORCID: https://orcid.org/0000-0002-1015-2564;
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