Borane Adducts of Hydrazoic Acid and Organic Azides: Intermediates for the Formation of Aminoboranes

Abstract

AbstractThe reaction of HN3 with the strong Lewis acid B(C6F5)3 led to the formation of a very labile HN3⋅B(C6F5)3 adduct, which decomposed to an aminoborane, H(C6F5)NB(C6F5)2, above −20 °C with release of molecular nitrogen and simultaneous migration of a C6F5 group from boron to the nitrogen atom. The intermediary formation of azide–borane adducts with B(C6F5)3 was also demonstrated for a series of organic azides, RN3 (R=Me3Si, Ph, 3,5‐(CF3)2C6H3), which also underwent Staudinger‐like decomposition along with C6F5 group migration. In accord with experiment, computations revealed rather small barriers towards nitrogen release for these highly labile azide adducts for all organic substituents except R=Me3Si (m.p. 120 °C, Tdec=189 °C). Hydrolysis of the aminoboranes provided C6F5‐substituted amines, HN(R)(C6F5), in good yields.