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Synthesis and Reactivity of Ruthenium Alkyl and Aryl Complexes and Their Application towards Aromatic C-H Bond Activation and Olefin Hydroarylation

by Lail, Marty A.

Abstract (Summary)
ABSTRACT Lail, Marty A., Synthesis and Reactivity of Ruthenium Alkyl and Aryl Complexes and Their Application towards Aromatic C-H Bond Activation and Olefin Hydroarylation (under the direction of T. Brent Gunnoe ). Herein we report on a Ru(II) system, TpRu(CO)(NCMe)(Ph) {Tp = hydridotris(pyrazolyl)borate} that activates the C-H bonds of aromatic substrates towards addition across unsaturated C-C bonds. Details of the mechanism of catalysis were elucidated both experimentally and computationally. In addition, the potential for an assymmetric RuIII complex seemed a promising route towards a more reactive hydroarylation catalyst and encouraged us to explore single-electron oxidation sequences of the Ru(II) complexes TpRu(L)(L?)(R) (L = CO, L??= NCMe, and R = Me or CH2CH2Ph; L = L??= PMe3 and R = Me). The putative Ru(III) systems [TpRu(L)(L?)(R)][OTf] (OTf = trifluoromethanesulfonate) undergo reductive elimination through bond homolysis and returns to formal Ru(II) oxidation states. We also sought to synthesize a second generation of Ru(II) scorpionate complexes, TpRu(L)(L?)R {L = phosphine, L? = phosphine or NCMe, R = Me or Ph} using phosphine ligands in place of CO which could activate C-H bonds and potentially serve as hydroarylation catalysts.
Bibliographical Information:

Advisor:Professor Paul Maggard; Professor Brent Gunnoe; Professor Jim Martin; Professor David Shultz

School:North Carolina State University

School Location:USA - North Carolina

Source Type:Master's Thesis

Keywords:chemistry

ISBN:

Date of Publication:08/14/2006

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