SusChEM: Group-Transfer Reactions of Low-Coordinate Metals

University Of Chicago, Chicago IL

Investigators

Abstract

With this award from the Chemical Synthesis (SYN) Program, Professor Gregory Hillhouse at the University of Chicago will carry out fundamental studies on the coordination and organometallic chemistry of low-coordinate first-row metals in various oxidation states. The primary objective of this work is to develop synthetic routes to new types of reactive late-transition metal complexes that can be used to carry out new atom- and group-transfer reactions that will enable efficient, atom-economical chemical transformations. These studies will help elucidate fundamental properties of inorganic molecules, particularly those with metal-ligand multiple bonds that stimulate novel reactivity. This chemistry will impact both stoichiometric and catalytic synthetic organic transformations. Group 10 metal complexes have widespread synthetic application in catalytic coupling reactions that form new carbon-carbon (C-C) and C-X single bonds, and this project will focus on developing useful methods for forming C=C, C=N, C=O, and C=S bonds (or other double bonds) utilizing nickel and other first-row metals. This research will explore, using experiment and theory, the coordination and organometallic chemistry of very low-coordinate metal complexes that form multiple bonds with imido and carbene ligands (LnNi=NR and LnNi=CR2), as well as non-traditional 2- and 3-coordinate open-shell, late-metal systems. This research will provide a solid, fundamental understanding of the chemistry of group transfer reactions involving metals that will impact applied areas of synthetic inorganic chemistry and catalysis, as well as organic synthesis and thus contribute to sustainability. In addition to the scientific contributions, this project will contribute to the training of the next generation of scientists and teachers by providing experience in interdisciplinary work, honing research skills, and exposure to both target-oriented and fundamental research that will empower coworkers to make transformative contributions to US chemical research endeavors. Specific activities directed toward education and outreach, with emphasis on the chemical challenges of the twenty-first century, are planned. The research team will include scientists at all educational levels: faculty, postdoctoral researchers, graduate, undergraduate, and high-school students. Participation of persons from underrepresented groups, which recently have included Hispanic, African-American, sight-disabled, and female coworkers, will be actively encouraged.