Shimeng Li, Yizhen Liu, Zuowei Xie
This work describes a general method for constructing unsymmetrical B(cage)-B single bond at room temperature via boron-centered carboranyl radicals. The approach enables the efficient utilization of both boron atoms from B2cat2 with very high yields. The key hypercoordinate boron radical intermediates are generated through a visible-light-driven Ni(I)/Ni(II) redox cycle employing zinc as the reducing agent. These radicals react directly with B2cat2 to form B─B bond, which can subsequently undergo further derivatizations including boronic ester formation and hydroxylation.