Electronic Thesis and Dissertation Repository

Degree

Master of Science

Program

Chemistry

Supervisor

Dr. Johanna Blacquiere

Abstract

The oxidation of C-H bonds to carbonyl functional groups using molecular oxygen (O2) is a desirable process as O2 is environmentally benign and inexpensive. However, oxidations that employ O2 have lower product selectivity, making it industrially unappealing. The metal complexes NiCl(π-cinnamyl)(NHC) oxidize stoichiometrically with O2 as the oxidant to selectively form the ketone and aldehyde products.

This thesis details the attempted catalysis with the NiCl(π-allyl)(NHC) complex and the stoichiometric reactivity of NiCl(π-allyl)(NHC) and NiCl(π-cinnamyl)(NHC) complexes upon O2 exposure. An investigation of the intermediate and decomposition species of the NiCl(π-allyl)(NHC) complex was conducted. The complexes were found to be non-catalytic under various conditions, and the decomposition studies revealed rapid, complex reactivity. Low-temperature studies and DFT methods determined the formation of two intermediates and lead to a new proposed mechanism. The first intermediate is proposed to be an organoperoxo metallocycle, while the second is proposed to be a µ-Cl dimer structure.

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