Prying open a Reactive Site for Allylic Arylation by Phosphine-Ligated Geminally Diaurated Aryl Complexes

Krista L Vikse; Athanasios Zavras; Tudor H Thoinas; Alireza Ariafard; George N Khairallah; Allan J Canty; Brian F Yates; Richard AJ O'Hair

Journal article

Prying open a Reactive Site for Allylic Arylation by Phosphine-Ligated Geminally Diaurated Aryl Complexes

Krista L Vikse, Athanasios Zavras, Tudor H Thoinas, Alireza Ariafard, George N Khairallah, Allan J Canty, Brian F Yates, Richard AJ O'Hair

ORGANOMETALLICS | AMER CHEMICAL SOC | Published : 2015

DOI: 10.1021/acs.organomet.5b00287

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Abstract

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..

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University of Melbourne Researchers

George Khairallah Author

Richard O'Hair Author Chemistry

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Awarded by ARC

Funding Acknowledgements

We thank the ARC for financial support via grant DP110103844 (to R.A.J.O. and G.N.K.), DP1096134 (to G.N.K), and DP150101388 (to R.A.J.O. and A.J.C.). The authors gratefully acknowledge the support of the University of Tasmania for a Visiting Scholarship (to A.A.) and the generous allocation of computing time from the Victorian Partnership for Advanced Computing (VPAC) Facility, the University of Tasmania and the National Computing Infrastructure.