Reactivity of a coordinated inorganic acetylene unit, HBNH, and the azidoborane cation [HB(N 3 )] +

thermolysis of a carbene-stabilized azidoborane. The reactivity of the fundamentally important HBNH unit (inorganic alkyne analogue) was explored in detail, including attempts to convert this species and related hydrido(azido)borane cations into molecular complexes of BN. This work provides added impetus for the development of molecular precursors that can release bulk boron nitride (a desirable insulator and thermal conductor) under mild conditions, and from solution.