Oxidative Addition of Alkenyl and Alkynyl Iodides to a Au^I Complex

The first isolated examples of intermolecular oxidative addition of alkenyl and alkynyl iodides to Au^I are reported. Using a 5,5′-difluoro-2,2′-bipyridyl ligated complex, oxidative addition of geometrically defined alkenyl iodides occurs readily, reversibly and stereospecifically to give alkenyl-Au^III complexes. Conversely, reversible alkynyl iodide oxidative addition generates bimetallic complexes containing both Au^III and Au^I centers. Stoichiometric studies show that both new initiation modes can form the basis for the development of C−C bond forming cross-couplings.