The Systematic Design of Nickel Complexes Toward Energy-Relevant Bond Activations

Abstract

The production of catalysts capable of the efficient and selective reactivity of CO2, H2, and CO toward useful products is required to lower global energy costs and allow for a sustainable carbon neutral future. To this end the design and synthesis of metal complexes capable of controlling the reactivity of these small molecules is highly desired. Bimetallic complexes allow for a greater chemical space allowing for high tailorability of metal catalyst properties presenting a new strategy for solving these issues. The tuning of a Z-type nickel-support bond toward small molecule reactivity unifies the chemistry described herein. In the introductory chapter the environmental and energy considerations motivating this work is made explicit. Inspired by enzymatic catalysis, a nickel-iron bimetallic complex for CO2 reduction to CO was studied in depth by NMR, Mössbauer, and electrochemical studies is detailed in Chapter 2. In Chapter 3 the role of a group 13 support on H2 binding and hydride transfer reactivity was investigated with the synthesis and characterization of a set of nickel-boron complexes. In Chapter 3 the combination of open ligand choice and metal support for the modulation of CO and CO2 binding was explored with iron and tin bimetallic nickel complexes.