Reactivity of Diruthenium Bisborylene Complexes: Formation of B-C and B-H Bonds via Borylene Ligand Coupling.

Thermal or photoinduced isomerization of diruthenium bridging bisborylene complexes [{Cp*(H)Ru}(μ-BAr)] (, Ar = Ph; , Ar = 3,4,5-FCH) led to -ruthenacarboranes and with newly formed B-C and B-H bonds. The reaction mechanism was analyzed by deuterium-labeling experiments and density functional theory calculations. Additionally, 2-fold B-H coupling between borylene and two hydrido ligands of can be achieved, assisted by Lewis base IPrMe to generate a dinuclear bridging borylene complex [(Cp*Ru)(μ-H)(μ-BPh)] (). Our results provide new reactivity patterns for borylene-based functionalizations.