RUI: Selective C-H and C-X Bond Activation to Platinum(II) and Reactivity of the Cyclometalated Complexes

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In this RUI project funded by the Chemical Structure, Dynamics and Mechanisms Program of the Chemistry Division, Professor Craig M. Anderson of Bard College will investigate the effect that ligand architecture has on the selectivity of carbon-hydrogen bond activation by platinum centers. He will examine selective carbon-hydrogen activation as a function of the ligand as a strategy for increasing control of desired products and improving processes as C-H activation has practical significance in commercial applications such as catalysis. Specifically, he plans to synthesize a variety of naphthyl and phenanthryl functionalized imine ligands in order to facilitate and/or drive the regioselectivity of C-H bonds mediated by platinum(II) centers. The newly formed cyclometalated platinum complexes will be characterized and studied for their reactivity. Ligands will be designed so that variables such as the ring size of the platinacycle formed, the bond hybridization of the C-H bond being activated, and aromaticity of the ring formed can be examined in detail. The resultant cyclometalated products will be studied in order to examine the factors affecting reductive elimination to produce C-C coupling as well as for their reactivity with various substrates.An important component of this work is that it will involve undergraduate student researchers at all levels. This includes the multi-step synthesis of ligands and complexes, the characterization of intermediates and products by IR, UV/Vis, emission spectroscopy, NMR, and XRD (X-ray diffraction) where possible, and the use of computational techniques to determine the kinetically and thermodynamically favored products in order to correlate theory with experimental results. The proposed research plans to establish a greater set of selectivity guidelines (especially in cases where several variables compete simultaneously), offer promise for the development of more selective catalytic processes, and contribute to the understanding of the intimate mechanisms of these processes. The activation of carbon-hydrogen bonds by metal complexes is important in the functionalization of available feedstocks into more useful products and materials, and is germane in the area of synthesis, for example, in carbon-carbon bond coupling.