CAS: Low-valent, highly catalytically active Ni-isocyanide compounds

Dr. Liviu M. Mirica of the Department of Chemistry at the University of Illinois Urbana-Champaign will investigate the role of the newly developed low-valent Ni-isocyanide compounds in chemical transformations and will establish the untapped potential of isocyanides as spectator ligands in organometallic catalysis. The project will impact how chemists assemble atoms to build complex molecules more efficiently, leading to innovative advanced manufacturing technologies that have a potential to create safe and secure products and processes with higher performance, fewer resources, and/or new capabilities. In addition, the research will combine synthetic inorganic/organometallic chemistry and physical inorganic spectroscopy, providing students with interdisciplinary training and the opportunity to develop a broad range of scientific skills. Dr. Mirica will continue to recruit and train young students for STEM fields through education and outreach activities focused on elementary and middle school students in the greater Urbana-Champaign area. Compared with Pd-mediated transformations, which generally employ diamagnetic intermediates, Ni systems can more readily undergo one-electron redox reactions, thereby enabling diverse reaction pathways. While reductive elimination from high-valent Ni centers is now a well-established process, the role of low-valent Ni species in cross-coupling catalysis has not been as thoroughly investigated because of the lack of readily available and thermally stable sources of Ni(I) with exchangeable ligands. This project will focus on the role of Ni(I) in cross-coupling catalysis by synthesizing and characterizing novel mononuclear and binuclear Ni(I) complexes with tert-butyl isocyanide ligands. The electronic structures and reaction pathways will be probed by combining infrared (IR) and ReactIR techniques, as well as utilizing accelerator X-ray sources from SLAC (Stanford Linear Accelerator Center) and Brookhaven National Laboratories. The reactivity and catalytic applications of the prepared complexes will then be systematically investigated in Suzuki-Miyaura cross-coupling reactions. The project has the potential to provide fundamental knowledge of relevance to design of catalytically active low-valent Ni-complexes. 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.