Gold can do it! The activation of disilanes at gold was observed experimentally and analyzed theoretically. Upon chelation with two or even only one phosphine donor, the oxidative addition of σ‐SiSi bonds proceeds readily at low temperatures. These results show an unexpected similarity between gold and the other late transition metals towards σ bond activation.

Over the last decades, our understanding of σ-bond activation at transition metals has progressed considerably from both fundamental and synthetic points of view thanks to the preparation and characterization of a variety of σ complexes. Here we report the synthesis and structural analysis of the first σ complex involving a coinage metal. The copper(I) complex 2 derived from the diphosphine-disilane [Ph(2)P(C(6)H(4))Me(2)Si-SiMe(2)(C(6)H(4))PPh(2)] (1) has been isolated and crystallographically characterized. The coordination of the Si-Si σ bond to copper was thoroughly analyzed by quantum-chemical methods.