Diazene Chemistry: Metal-Free Models of N<sub>2</sub> Reduction Intermediates
Zahid Hussain, Yong-an Luo, Yile Wu, Zheng‐Wang Qu, Stefan Grimme, Douglas W. Stephan
Abstract
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 ( t BuO 2 CN) 2 block initial interaction of B(C 6 F 5 ) 3 with nitrogen and prompt loss of methylpropene and CO 2 to diazene (N 2 H 2 ) borane adduct 1 and the analogous hydrazine (N 2 H 4 ) adduct 2 . These species react with basic phosphines to give anions of 3 and 5 containing N 2 H and N 2 H 3 fragments, respectively. While these species are not derived directly from N 2, they represent metal-free species containing N 2 H n ( n = 1–4) fragments, which model plausible intermediates in the reduction of N 2 .