Grant: Discovery Grants Program - Individual

The pursuit of mild and selective synthetic methods is a persistent challenge that spans organic, inorganic, and polymer/materials chemistry. The central role that metal catalysts play in the discovery and development of such methods was recognized in the awarding of the 2001 and 2005 Nobel Prizes in Chemistry. Appropriately constructed late metal (groups 7-11) catalysts are able to activate (i.e. induce reactivity in) typically unreactive fragments such as E-H bonds (E = H, C, Si, N, P, etc.); advancements in the design of E-H activation catalysts has given rise to myriad synthetic processes that are employed widely for the conversion of simple substrates into value-added products, ranging from chiral pharmaceuticals to unusual polymers. Still, no universally effective catalyst for E-H activation exists, and important challenges remain, including: (i) the development of catalysts that function in high- and low-polarity media; (ii) the general incorporation of sp3 C-H activation into catalytic cycles; and (iii) the establishment of tandem reactions involving double geminal E-H activation. My group targets new late metal complexes that, by virtue of their unique construction, can mediate challenging E-H activation reactions; we seek catalysts that offer unusual chemo-, regio-, and enantioselectivity, as well as those that operate under conditions in which traditional cationic late metal catalysts are not effective. Key questions that we seek to address include: (i) Can we develop effective neutral (including zwitterionic) alternatives to traditional cationic catalysts? (ii) What advantages might be brought about by the use of late metals that are not typically employed in E-H activation catalysis? (iii) How can we design late metal complexes that activate two E-H bonds in a single substrate? (iv) How might we incorporate new or improved E-H activation chemistry into useful catalytic (and possibly enantioselective) processes? Potential applications of the reactivity under investigation in my group range from organic synthesis, to the development of effective hydrogen storage/generation techniques, to the preparation of main-group polymers.