Metal–metal redox synergy in selective B–H activation of ortho-carborane-9,12-dithiolate

New o-carborane-9,12-dithiolate dirhodium complexes are reported to selectively activate inert B-H bonds of o-carboranes to form B-X bonds by using water, alcohols, and alkylhalides (<60 °C, yields >80%). Characterization of the key intermediates demonstrates an oxidative addition and reductive elimination pathway via metal-metal cooperativity.