General Preparation of (N 3 N)ZrX (N 3 N = N(CH 2 CH 2 NSiMe 3 ) 3 3− ) Complexes from a Hydride Surrogate

作者：A.J. Roering, A.F. Maddox, L.T. Elrod, Stephanie M. Chan, Michael B. Ghebreab, K.L. Donovan, Jillian J. Davidson, Russell P. Hughes, T. Shalumova, Samantha N. MacMillan, Joseph M. Tanski, Rory Waterman · 发表于：Organometallics · 年份：2008 · DOI：10.1021/om8008684 · 被引用次数：40 · 研究领域：Asymmetric Hydrogenation and Catalysis、Organometallic Complex Synthesis and Catalysis、Coordination Chemistry and Organometallics

A homoleptic triamidoamine zirconium complex featuring a metalated trimethylsilyl substituent, [κ 5 -(Me 3 SiNCH 2 CH 2 ) 2 NCH 2 CH 2 NSiMe 2 CH 2 ]Zr ( 1 ), was synthesized by reaction of Zr(CH 2 Ph) 4 with N(CH 2 CH 2 NHSiMe 3 ) 3 followed by sublimation. Complex 1 is a general precursor to a family of complexes with the formulation (N 3 N)ZrX (N 3 N = N(CH 2 CH 2 NSiMe 3 ) 3 3−, X = anionic ligand) by reactions that parallel expected reactivity of a hydride derivative. Treatment of 1 with phosphines, amines, thiols, alkynes, and phenol resulted in the formation of new, pseudo- C 3 v -symmetric (N 3 N)ZrX complexes (X = phosphido, amido, alkynyl, thiolate, or phenoxide) via element−H bond activation. Thus, the reactivity of complex 1 is that best described as a hydride surrogate . For example, complex 1 reacted with PhPH 2 at ambient temperature to provide (N 3 N)ZrPHPh ( 2 ) in 86% yield. Density functional theory studies and X-ray crystal structures provide a general overview of the bonding in these complexes, which appears to be highly ionic. In general, there is little evidence for ligand-to-metal π-bonding for the pseudoaxial X ligand in these complexes except for strongly π-basic terminal amido ligands. The limited π-bonding appears to be the result of competitive π-donation by the pseudoequatorial amido arms of the triamidoamine ancillary ligand. Thus, the relative Zr−X bond energies are governed by the basicity of the anionic ligand X. Solid-state structures of pho...