Reduction of (Formazanate)boron Difluoride Provides Evidence for an N‑Heterocyclic B(I) Carbenoid Intermediate

Despite the current interest in structure and reactivity of sub-valent main group compounds, neutral boron analogues of N-heterocyclic carbenes have been elusive due to their high reactivity. Here we provide evidence that 2-electron reduction of a (formazanate)­BF2 precursor leads to NaF elimination and formation of an N-heterocyclic boron carbenoid, and describe the formation of a series of unusual BN heterocycles that result from trapping of this fragment. Subsequent chemical oxidation by XeF2 demonstrates that the trapped (formazanate)B fragment retains carbenoid character and regenerates the boron difluoride starting material in good yield. These results indicate that the formazanate ligand framework provides a unique entry into sub-valent boron chemistry.