Oxidative Processes of Bimetallic Nickel Complexes Utilizing Redox Active Ligands

Douglas R Hartline, Purdue University


The utilization of metal–metal bonds for novel chemical transformations is an area of research which remains largely unexplored. This is, in part, due to the instability of metal-metal single bonds following oxidative processes typically leading to complex decomposition. Through the use of a binucleating redox active ligand it is possible to stabilize these metal–metal bonds through the release of electron density from the ligand. The motion of these electrons results in no net oxidation state change to the metal centers. This dissertation will discuss the use of a binucleating redox active ligand to probe the effects of nuclearity on enyne coupling reactions allowing for the isolation of Pauson-Khand type intermediates. It was also determined that enyne couplings experience a rate acceleration resulting from the bimetallic transition state of invoked in this reaction. These bimetallic complexes are also amenable to the bond activation of norbornadiene Csp2–Csp3 bonds. Following the activation of these C–C bonds catalytic turnover of these complexes can be achieved using metal carbonyls as stoichiometric carbon monoxide surrogates to produce novel complexes. This dissertation will also explore the effects of single electron oxidation on these complexes and the resulting changes on substrate reactivity.




Uyeda, Purdue University.

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