Diazene Chemistry: Metal-Free Models of N2 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 (tBuO2CN)2 block initial interaction of B­(C6F5)3 with nitrogen and prompt loss of methylpropene and CO2 to diazene (N2H2) borane adduct 1 and the analogous hydrazine (N2H4) adduct 2. These species react with basic phosphines to give anions of 3 and 5 containing N2H and N2H3 fragments, respectively. While these species are not derived directly from N2, they represent metal-free species containing N2H n (n = 1–4) fragments, which model plausible intermediates in the reduction of N2.