Migratory Insertion of CO into a Au-C Bond.

A MeDalPhos-ligated gold(III) metallafluorene complex, generated via C-C oxidative addition of biphenylene, reacts with CO to produce 9-fluorenone. Experimental and computational studies show that this proceeds via a hitherto unknown migratory insertion of CO into a Au(III)-C bond. This process is more energetically challenging compared to other M-C bonds, but once achieved, the product is comparatively stable with respect to retro-carbonylation. Exploiting migratory insertion of CO into Au-C bonds may extend the range of products that are accessible using gold chemistry.