American Chemical Society, Organometallics, 13(34), p. 3255-3263, 2015
DOI: 10.1021/acs.organomet.5b00287
Full text: Download
Gas-phase ion–molecule reaction experiments, theoretical kinetic modeling, and computational chemistry were used to examine the role of a second gold center in promoting allylic arylation. Geminally diaurated complexes [(L)nAu2Ph]+ are demonstrated to participate in C–C bond formation reactions with allyl halides, CH2═CHCH2X (X = Cl, Br, and I), given a favorable phosphine ligand architecture. Thus, while [(Ph3P)2Au2Ph]+, 1, is unreactive toward the allyl halides, [(dppm)Au2Ph]+, 2 (where dppm = bis(diphenylphosphino)methane, (Ph2P)2CH2), reacts via C–C bond coupling to produce [(dppm)Au2X]+. The reaction kinetics (efficiencies) follows the expected leaving group ability, X = I (58%) > Br (2%) > Cl (0.02%). DFT calculations were carried out to examine the potential mechanism for the C–C bond coupling reactions of 2 with each of the three allyl halides. The most favorable mechanism for C–C bond coupling of 2 requires the active participation of both gold centers in a redox couple mechanism wherein the allylic halide oxidatively adds across the gold centers to form a AuIAuIII complex with a weak Au···Au interaction, followed by intramolecular reductive elimination of allyl benzene from the AuIII center.