Advances in divalent and trivalent organonickel chemistry: new routes to C-H functionalizations

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This application requests funds from NSERC for an innovative scientific research program in organometallic and inorganic chemistry to be carried out in the applicant's laboratory, which is located at the department of chemistry, Université de Montréal. The studies we propose to conduct are primarily curiosity-driven experiments aimed at advancing our fundamental knowledge of the chemical nature and reactivities of complex molecules consisting of a nickel atom bonded to other chemical elements contained within a stabilizing entity called “pincer” ligands. These complex molecules, or complexes for short, adopt discrete structures and geometries dictated by a combination of the pincer ligand's bonding, steric and electronic properties, as well as the nickel atom's valence, i.e., formal degree of ionization. The reciprocal influence of the ligand and the metal centre on each other often gives rise to novel chemical behaviour that a chemist can harness for a various purposes, including for practical applications in fields as diverse as petrochemicals, plastics, pharmaceuticals, and other useful materials. Thus, the program we propose is designed to lead to scientific discoveries, but it also contains elements that can be exploited for commercial and societal gains. The creative ideas for this research program evolved from our laboratory's previous studies, which were also funded by NSERC. The observations we made during these studies allowed us to elaborate synthetic routes to novel organonickel complexes, including a few complexes in which the central nickel atom is in a reactive trivalent state. Careful explorations of the reactivities of these complexes revealed new routes leading to “cross-coupling” protocols, an outcome that holds much promise for developing practical methodologies for making new, useful materials. The proposed work will take our studies in exciting new directions that we anticipate will result in unanticipated discoveries and useful inventions. Since the proposed experiments will be conducted by our students at the B. Sc., M. Sc., and Ph. D. level, our research program will also result in the training of many young scientists. Therefore, the funds we seek will allow us to nurture highly qualified personnel who will go on to valuable careers in scientific research and development. Our previous studies have already trained dozens of young students who occupy many leading scientific-technical positions in universities, colleges, research centers and industry. In this sense, NSERC funds enable novel discoveries and innovations while serving as solid investments in the training of future scientists and technologists.