The Uncommon Reactivity of Dihapto-Coordinated Nitrile, Ketone, and Alkene Ligands When Bound to a Powerful π-Base
Organometallics2006Vol. 25(21), pp. 5051–5058
Citations Over TimeTop 14% of 2006 papers
E.C. Lis, David A. Delafuente, Yunqing Lin, Christopher J. Mocella, M.A. Todd, Weijun Liu, Michal Sabat, William H. Myers, W. Dean Harman
Abstract
A series of complexes of the form TpM(NO)(L')(η2-L) are prepared (where L is a nitrile, ketone, or alkene, M = W or Mo, L' = PMe3, MeIm, Tp = hydridotris(pyrazolyl)borate). These complexes are subjected to various electrophiles (e.g., alkyl halides, Brønsted acids) to systematically probe the ability of the π-basic transition metal to affect the reactivity of the dihapto-coordinated ligand. Alkylation is observed at the heteroatom of the ketone and the nitrile, but depending on the reagent, alkylation of the nitrosyl ligand or addition to the complexed π-bond also occurs. The structures of several nitrilium complexes and a rare example of an η2-acetonium complex are also reported.
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