Diazene Chemistry: Metal-Free Models of N 2 Reduction Intermediates

Interest in main group chemistry related to the Haber-Bosch process has drawn less attention than that of transition metal species. Herein, we show that the steric demands in ( BuO CN) block initial interaction of B(C F ) with nitrogen and prompt loss of methylpropene and CO to diazene (N H ) borane adduct and the analogous hydrazine (N H ) adduct . These species react with basic phosphines to give anions of and containing N H and N H fragments, respectively. While these species are not derived directly from N , they represent metal-free species containing N H ( = 1-4) fragments, which model plausible intermediates in the reduction of N .