Document Type

Honors Project On-Campus Access Only

Comments

A special thanks to my advisor Professor Paul J. Fischer for accepting me into his lab during the summer 2014, and for providing invaluable support and guidance in the preparation of this thesis.

Thank you to my coworkers Trent D. Bohrmann and Hanyue Xu for making the summer 2014 research both enjoyable and productive.

Abstract

We have found that tris(diphenylphosphinomethyl)phenylborate (PhBP3) makes stable complexes with zerovalent group VI metals of the form [Et4N][M(CO)3(PhBP3)] (M = Cr (1) , Mo (2), and W (3)). We also report the zwitterionic complex Mn(CO)3(PhBP3) (4). The apparent resistance of 2 and 3 towards two-electron oxidation by Br2 and I2 suggests that PhBP3 may not donate enough electron density to the Mo(0) and W(0) centers to replace tris(pyrazolyl)borates in zerovalent group VI metal π-basic dearomatization agents. The most remarkable finding of this work is the discovery of a new binding mode in PhBP3, in which one metal tricarbonyl fragment binds to the phosphines in a typical κ3 fashion, while another metal tricarbonyl fragment binds η6 to the borate phenyl substituent. Coordinating a metal in this way inductively decreases the amount of electron density at the phosphine-bound metal, creating a novel method for donation modulation of PhBP3 at phosphorous.

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