RUI: CAS-SC: Promoting Group-Transfer Reactions at Metal/Main-Group Bonds

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With support from the Chemical Synthesis Program of the Chemistry Division, Matthew T. Whited and his research group of undergraduate students at Carleton College are developing new applications of metal complexes featuring bonds to heavy non-metal elements such as silicon. These compounds are designed to provide synergistic interaction between the main group atom and the metal. This enables the compound to bring together different groups and enable reactions between them. The project will develop systems where reactive chemical fragments are attached to inexpensive and readily abundant substrates to afford products with applications in both that bulk and fine chemical arenas. This approach also seeks to replace expensive, rare metals with earth abundant ones in catalysis. The project will provide a training ground for undergraduate researchers and enable expanded outreach to high school students in Northfield, MN and Faribault, MN on topics related to chemical synthesis and X-ray crystallography.This project seeks to develop the chemistry of late-metal/main-group interactions by exploring metal-silicon single and multiple bonds as platforms for transfer of reactive nitrene, carbene, and related groups to organic substrates. Preliminary findings have shown that these “electronically frustrated” linkages can enable dual-site catalysis whereby the two sites (metal and main-group element) interact with different substrates to bring them together, but the generality of this strategy has not been demonstrated. Such an approach serves to avoid problems of poisoning present in many catalysts and also provides a distinct approach to using earth abundant metals such as iron, cobalt, and nickel in group-transfer catalysis.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.