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 (tBuO 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 .

Reactions of the boranes, BH(C6F5)2 or 9-BBN, with azodicarboxylates or an azodicarbonylamide provide facile access to NBO heterocyclic compounds. The products [C6F5)2BOC(X)N]2 X = OEt, 1, OiPr 2, OCH2Cl3C 3,...

The stannyl phosphaketene (CH{(CMe)(2,6-iPr2C6H3N)}2)SnPCO 1 is shown to act as a synthon for phosphorus analogues of β-lactam in the presence of E(C6F5)3 (E = B or Al). The [2+2] addition...