Inspiration, Frustration, and Fascination: An Excursion into Low-Oxidation State Main Group Chemistry

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In this project funded by the Chemical Synthesis Program of the Chemistry Division, Professor Gregory H. Robinson of the Department of Chemistry at The University of Georgia will pursue an ambitious program to explore challenging areas of low-oxidation state main group chemistry. The work will demonstrate that N-heterocyclic carbenes and their N-heterocyclic dicarbene derivatives constitute a unique platform from which many unusual low-oxidation state main group species may be obtained. Major goals in the proposed work include: (a) the synthesis of unusual species containing one-coordinate borocations; (b) the synthesis of two-coordinate borylenes; (c) the carbene-stabilization of a Si(0) atom and a parent silylene; and (d) the preparation of extended molecular systems integrated with main group diatomic allotrope moieties. These targeted low-oxidation state species may further be utilized in the synthesis of other unusual main group molecules such as NHC-stabilized boron analogs of carbonyl derivatives.This project utilizes a class of organic bases to stabilize highly reactive diatomic molecules such as disilicon, diphosphorus, and diarsenic at room temperature. This proposal describes efforts to further study the synthesis, structure, and reactivity of these base-stabilized diatomics. It is possible that these base-stabilized diatomics may have applications related to new ways to deposit elemental silicon or phosphorus in the fabrication of advanced electronics and computer chips and chemical catalysis. Indeed, Professor Robinson and coworkers were recently granted a US patent (No.: 8278456) for their discovery of using organic bases to stabilize diatomic molecules.