Carbon-Carbon Bond Formation and Related Reactions on Metal Oxides: Surface Science and Catalysis

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ABSTRACT Mark Barteau CTS-9410965 This is an investigation of two carbon-carbon bond-forming reactions that occur on metal-oxide surfaces: reductive carbonyl coupling and alkyne cyclotrimerization. It has been demonstrated that both reactions can be run as gas-solid reactions on titania single crystals even in ultrahigh vacuum. This research defines the mechanisms of these surface reactions in order to test analogies with liquid-phase organometallic reactions, and applies the understanding gained to the invention of new heterogeneous catalysts for novel surface organic syntheses. The program includes spectroscopic investigations of carbon-carbon bond-forming reactions on reduced titania single crystals, steady-state and temperature-programmed flow reactor studies on oxide powders at atmospheric pressure (to demonstrate the "scale-up" from ultrahigh vacuum to normal industrial catalytic operations), and scanning probe microscopy experiments to probe active sites and adsorbed intermediates at the molecular level and to test the ability to manipulate these factors. This effort is the centerpiece of a program to enable the transfer of traditionally esoteric surface chemistry to industrial practice through a series of "scale-up" stages, and thus rationalize the introduction of new catalytic chemistry into industrial technology. ***