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Prying open a reactive site for allylic arylation by phosphine-ligated geminally diaurated aryl complexes


Vikse, KL and Zavras, A and Thomas, TH and Ariafard, A and Khairallah, GN and Canty, AJ and Yates, BF and O'Hair, RAJ, Prying open a reactive site for allylic arylation by phosphine-ligated geminally diaurated aryl complexes, Organometallics, 34, (13) pp. 3255-3263. ISSN 0276-7333 (2015) [Refereed Article]

Copyright Statement

Copyright 2015 American Chemical Society

DOI: doi:10.1021/acs.organomet.5b00287


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.

Item Details

Item Type:Refereed Article
Keywords:gold, organogold, couplingreactions, computational, mas spectrometry
Research Division:Chemical Sciences
Research Group:Inorganic chemistry
Research Field:Organometallic chemistry
Objective Division:Expanding Knowledge
Objective Group:Expanding knowledge
Objective Field:Expanding knowledge in the chemical sciences
UTAS Author:Ariafard, A (Associate Professor Alireza Ariafard)
UTAS Author:Canty, AJ (Professor Allan Canty)
UTAS Author:Yates, BF (Professor Brian Yates)
ID Code:104951
Year Published:2015
Web of Science® Times Cited:7
Deposited By:Chemistry
Deposited On:2015-11-30
Last Modified:2017-10-25

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