New Ligand Designs for Homogeneous Catalytic Nitrogen Fixation

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One of the unmet challenges in chemistry is the*discovery of an efficient yet mild process for the conversion of molecular*nitrogen (N2) into higher value organo-nitrogen containing species,*such as amines or nitrogen-containing heterocycles. The well-known production of ammonia via the Haber-Bosch process is over 100 years old,*and is still the only process that uses N2 as a feedstock on an*industrial scale. In*contrast, the isoelectronic CO molecule is used in a variety of different*industrial processes, such as hydroformylation, the acetic acid synthesis, and*carbonylation. The fact*that even after more than 100 years there is still no new industrial process that*uses molecular nitrogen as a feedstock is a reminder of the difficulty of*the problem of using this unreactive small molecule in an industrial setting.****** This proposal seeks to both discover and optimize catalytic reactions that convert molecular nitrogen into higher-value organic materials. We have made seminal contributions to stoichiometric activation of dinitrogen (N2) that have spanned almost three decades. However, recently, we have discovered a unique catalytic system that very efficiently converts N2 into N(SiMe3)3 with turnover numbers that rival the best reports from other researchers world-wide. Building on this exciting result is the focus of the ideas presented in this Discovery Grant application. Not only do we want to optimize this process by examining new ligand designs and new base metal combinations, but we also want to expand this reaction to generate nitrogen-carbon bonds catalytically by building on mechanistic studies of the aforementioned catalytic formation of N(SiMe3)3. Success in this project will be in the form of publications in high-impact journals and the continued training of highly qualified personnel who will be ready to tackle important chemical problems of societal importance.