Journal
ORGANOMETALLICS
Volume 34, Issue 13, Pages 3255-3263Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.organomet.5b00287
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Funding
- ARC [DP110103844, DP1096134, DP150101388]
- University of Tasmania
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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)(n)Au2Ph](+) 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)(2)Au2Ph](+), 1, is unreactive toward the allyl halides, Rdppm)Au2Ph](+), 2 (where dppm = bis(diphenylphosphino)methane, (Ph2P)(2)CH2), 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 (AuAuIII)-Au-I complex with a weak Au center dot center dot center dot Au interaction, followed by intramolecular reductive elimination of allyl benzene from the Au-III center.
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