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Insertion of Acetonitrile into the Zr−P Bond of [Cp°2ZrCl(PHCy)] (Cy = Cyclohexyl, Cp° = η5-C5EtMe4) Followed by PHCy Elimination To Give [Cp°2(Cl)Zr(μ-NCMe−CMeN)Zr(Cl)Cp°2]

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posted on 19.07.1999, 00:00 by Ulrike Segerer, Steffen Blaurock, Joachim Sieler, Evamarie Hey-Hawkins
[Cp°2ZrCl(PHCy)] (Cy = cyclohexyl, Cp° = η5-C5EtMe4) undergoes insertion of MeCN into the Zr−P bond, yielding [Cp°2ZrCl{NC(Me)(PHCy)}] (1). Isomers with a Z (1a) or E (1b) configuration at the C−N double bond are obtained in a ratio of 13:1. At room temperature, 1 slowly decomposes in solution with elimination of a PHCy fragment and formation of [Cp°2(Cl)Zr(μ-NCMe−CMeN)Zr(Cl)Cp°2] (2). Two isomers are obtained with a trans (2a) or cis (2b) arrangement around the C−N double bonds of the bridging butane-2,3-diimino(2-)-N,N‘ ligand. 1a, 2a, and 2b were isolated and characterized by IR, MS, and NMR spectroscopy (1H, 31P, 13C), and crystal structure determinations were carried out on 1a and 2a. In the solid state, the short Zr−N bonds and the almost linear Zr−N−C angles of 1a and 2a indicate the presence of Zr−N double bonds.