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

KL Vikse; A Zavras; TH Thomas; A Ariafard; GN Khairallah; AJ Canty; BF Yates; RAJ O'Hair

Journal article

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

KL Vikse, A Zavras, TH Thomas, A Ariafard, GN Khairallah, AJ Canty, BF Yates, RAJ O'Hair

Organometallics | AMER CHEMICAL SOC | Published : 2015

DOI: 10.1021/acs.organomet.5b00287

Download PDF

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..

View full abstract

University of Melbourne Researchers

Richard O'Hair Author

Related Projects (2)

Coinage metal nanoclusters: synthesis, structure and reactivity

Metal catalysts play important roles in the multi-billion dollar production of many industrial and fine chemicals used in wide-ranging appli..

Decarboxylation to unmask organometallics: scope and utility in bond formation

Carboxylic acids are valuable in the synthesis of biologically and industrially important compounds. The promise of developing eco-friendly ..

Grants

Awarded by Australian Research Council

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.