Pseudodiborenes: hydride-bridged diboranes(5) as two-electron reductants of chalcogens.

The reactivity of two nucleophilic neutral sp(2)-sp(3) diboranes towards chalcogens is presented herein. Both diboranes(5) serve as two-electron reductants, incorporating oxygen, sulfur and selenium atoms. Treatment with chalcogen sources results in the oxidative insertion of one chalcogen atom into the B-B single bond, while depending on the negative inductive effect of the chalcogen and the boron bound aryl substituent further N-heterocyclic carbene (NHC) ring expansion and hydride migration can occur. These reactions provide access to unprecedented six- or seven-membered heterocycles and help to illuminate the pseudo-multiple bonding character of hydrogen-bridged B-B single bonds.