Exploring New Reactivity Enabled By 3d Metal Carbene Complexes in Weak-Field Bis(alkoxide) Ligand Environments

Wayne State University, Detroit MI

Investigators

Abstract

With the support of the Chemical Synthesis program in the Division of Chemistry, Professor Stanislav Groysman of Wayne State University, Professor Richard L. Lord of Grand Valley State University and their students will develop new synthetic routes towards organic molecules of importance to the pharmaceutical industry such as cyclopropanes, azetidinimines, and ketenimines. The proposed molecular targets constitute key chemical fragments of existing drugs or drug candidates (cyclopropanes), can potentially revolutionize the field of antibiotic resistance (azetidinimines), and serve as reactive precursors of choice to the synthesis of pharmaceuticals (ketenimines). Using their combined expertise in synthetic chemistry (Groysman lab), computational chemistry (Lord lab), and catalysis (both labs), this collaborative research program aims to design new transition metal compounds containing reactive carbene fragments, and probe their propensity for new chemical reactions that are sustainable and efficient. An important educational goal of the close collaboration between the synthetic and the computational groups is to afford more comprehensive undergraduate and graduate education in inorganic chemistry. As an important part of this collaborative research program, the Groysman and Lord groups will conduct comprehensive training of chemistry professionals at all levels to help train the future workforce. Transition metal carbene complexes are among the most effective synthetic tools to create new C-C bonds, and there is a significant interest in developing new synthetic transformations mediated by sustainable metal carbenes. In this project, the collaborative synthetic (PI Groysman) and computational (co-PI Lord) research team will investigate the C-C bond formation reactivity of a new family of middle/late 3d transition metal carbene complexes supported by bulky weak-field bis(alkoxide) ligands. The central hypothesis is that the radical nature of the carbene functionality in the bis(alkoxide) transition metal-carbene species, combined with the coordinative unsaturation at the metal, will allow efficient C-C bond formation with various substrates including isocyanides (to form ketenimines) and olefins (to form cyclopropanes). The research goals include advancing the fundamental chemistry of middle and late 3d metal-carbene complexes, and harnessing the reactivity of those complexes to develop sustainable syntheses of valuable reactive functionalities including ketenimines, cyclopropanes, azetidinimines, and oxetanimines. 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.