Synthesis and Small-Molecule Reactivity of Unsaturated Metal Isocyanides

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In this project funded by the Chemical Synthesis program of the Chemistry Division, Professor Joshua S. Figueroa of The University of California, San Diego is studying the synthesis and fundamental reactivity of coordinatively unsaturated transition metal isocyanide complexes. The isocyanide molecules that will be utilized in this project represent a class with significant steric encumbrance, such that they are effective at stabilizing highly electronically and coordinatively unsaturated transition metal centers. The proposed work focuses on the interplay between the reactivity of low-coordinate complexes and isocyanide ligand super-structure for the goal of developing new reactivity paradigms in transition metal chemistry and homogeneous catalysis. In addition, this project is also ideally suited for outreach and training at all levels of the STEM education continuum. The PI is engaged in increasing participation of underrepresented persons (URP) in research to expose young students to STEM fields and careers. The synthetic work is integrated into major outreach efforts of the PI aimed at increasing the exposure, participation and retention of under-represented persons in synthetic chemistry and related STEM fields. These efforts include increasing the participation of junior college transfer students in the San Diego area in chemical research and continued chemistry enrichment activities for local San Diego High School students with predominantly URP backgrounds.This project focuses on the synthesis and study of low-coordinate transition metal isocyanide complexes in order to advance fundamental aspects of molecular design, small-molecule activation chemistry and catalysis. Specific studies are proposed to intimately control the electronic structure environment of transition metal centers, through synthesis, for the binding and activation of exceedingly unreactive small molecule substrates and difficult-to-activate chemical bonds. A complement of synthetic strategies and molecular design principles are proposed to achieve these goals. In addition, the synthetic work is coupled with advanced spectroscopic, analytical, mechanistic and computational techniques to provide insight into electronic-structure/reactivity correlations.