Bismuth Amides Mediate Facile and Highly Selective Pn–Pn Radical?Coupling Reactions (Pn=N, P, As)

The controlled release of well-defined radical species under mild conditions for subsequent use in selective reactions is an important and challenging task synthetic chemistry. We show here that simple bismuth amide [Bi(NAr2)3] readily aminyl radicals [NAr2]. at ambient temperature solution. These yield the corresponding hydrazines, Ar2N?NAr2, as a result highly N?N coupling. exploitation facile homolytic Bi?Pn bond cleavage Pn?Pn formation was extended to higher homologues pnictogens (Pn=N–As): homoleptic amides mediate dehydrocoupling HPnR2 give R2Pn?PnR2. Analyses by NMR EPR spectroscopy, single-crystal X-ray diffraction, DFT calculations reveal low Bi?N bond-dissociation energies, suggest coupling coordination sphere bismuth, electronic steric parameters effective tools control these reactions.