Abstracts Category : Other

Investigation of Thermal Products from Photochemically Generated Intermediates of a Diiron-Diphosphine Complex; Relevance to FeFe-Hydrogenase

by Anne Elizabeth Nelson

The biohydrogen cycling enzymes known collectively as hydrogenases are shaping the vision of industrial hydrogen catalysis. This family of enzymes reversibly oxidizes molecular hydrogen. Inorganic structural and functional models of the [FeFe]-hydrogenase active site provide a convenient and simple approach to studying changes that mimic the active site chemistry. Presented herein, (??-pdt)[Fe(CO)2(PMe3)]2 ([2]) and {??-H(??-pdt)[Fe(CO)2(PMe3)]2[PF6]} ([2H]+) were photochemically altered to observe thermal changes specific to various solvent and solute mixtures.In this study continuous wave photolysis was used to generate reactive intermediates in organic solutions. The resulting thermal chemistry was monitored by infrared and ultraviolet-visible spectroscopy.It was determined that the photochemically generated CO unsaturated photoproducts of [2] and [2H]+ thermally combine with solvent or dissolved CO producing semi-stable complexes in solution.This work supports the hypothesized irradiation-dependent CO loss and offers evidence for the correlation between solvent or solutes and stability of thermal products.Advisors/Committee Members: Works, Carmen, Ph.D. (advisor), Nelson, Anne Elizabeth (sonomaauthor), Whiles, Jennifer, Ph.D. (committee member).