LAUSR

We report herein the synthesis of a bisphosphine-[NHC-BH3] compound and its coordination toward gold. The ligand is shown to support a bimetallic structure bisphosphine-[NHC-BH3](AuCl)2. The abstraction of one chloride from the gold metal center triggers the activation of a BH3 fragment, leading to the reductive elimination of H2 and the formation of a dicationic Au42+ complex featuring Au centers at the +0.5 oxidation state, via a (μ-H)Au2 intermediate, characterized in situ at 183 K. The reactivity of Au4 with thiophenol led to the reoxidation of the gold metal centers to a (μ-S(Ph))Au2 complex. In the different complexes, borane fragment was shown to bridge the Au2 core via weak interaction with [BH], [BCl], and [BH2] moieties.