Energetics and Mechanisms of Organometallic Reactions Relevant to the Functionalization of Alkanes

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This award in the Inorganic, Bioinorganic, and Organometallic Chemistry program provides continued support for studies on the energetics and mechanisms of organometallic reactions relevant to the functionalization of alkanes by Dr. Karen I. Goldberg, Department of Chemistry, University of Washington. This project involves studies on the Pt(II)/Pt(IV) couple as a general model for d8 square planar and d6 octahedral compounds as well as for the catalytic potential of this couple for alkane functionalization. Mechanistic and kinetic investigations of oxidative addition of C-H and C-C bonds to Pt(II) and reductive elimination of C-X (X = heteroatom, H, or C) bonds from Pt(IV) will be carried out. Mechanistic studies will also be performed to determine the ideal ligand/metal environment required to promote the oxidation of Pt(II) alkyls by water or alcohols to form Pt(IV) alkyl hydroxides or alkoxides and hydrogen. The reactivity of Pt(IV) alkoxides will also be explored as representative of high valent late transition metal alkoxides. The reactivity of an open coordination site on Pt(IV) will be examined. Such a site is necessary for reductive elimination reactions and may also be useful for functionalization. Possible coordination and insertion of small organic molecules and C-H activation by the open site will be explored. This project will give fundamental information on the activation and functionalization of alkanes and provide possible new transition metal catalysts for this important reaction. Alkanes represent a considerable portion of our natural gas and petroleum resources. The potential of these enormous reserves for use in large scale chemical syntheses is limited by the very unreactive nature of the alkane C-H and C-C bonds. Transition metals have been shown to be capable of activating the C-H bonds in alkanes and homogeneous transition metal catalysis is viewed as a promising solution to the conversion of alkanes selectivity into more usable organic products, such as the conversion of methane into methanol.