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Computational study of selectivity in the [PtIICl4]2−-catalysed arylation of arenes by diaryliodonium reagents: arene activation at PtIV centres

Citation

Canty, AJ and Ariafard, A, Computational study of selectivity in the [PtIICl4]2−-catalysed arylation of arenes by diaryliodonium reagents: arene activation at PtIV centres, Dalton Transactions, 46 pp. 15480-15486. ISSN 1477-9226 (2017) [Refereed Article]


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DOI: doi:10.1039/c7dt03602g

Abstract

The mechanism for the [PtIICl4]2−-catalysed reaction of Ph2IIII(TFA) (TFA = trifluoroacetate) with naphthalene (NapH) to give β-phenylation over α-phenylation of naphthalene has been examined by computational methods. In support of the mechanism proposed by Sanford based on experimental evidence, reaction commences by oxidative phenyl transfer from [Ph2I]+ to [PtIICl4]2−, giving trans-[PhPtIVCl4(TFA)]2−. Transformation to cis-[PhPtIVCl3(TFA)] leads to reaction with NapH at the β-position in an inner-sphere Concerted Metalation Deprotonation (CMD) manner to give cis-[Ph(Nap)PtIVCl3] and trifluoroacetic acid. Reductive elimination yields β-PhNap, and coordination of chloride regenerates [PtIICl4]2− for subsequent catalytic cycles. The selectivity for β-phenylation over α-phenylation is attributable to steric factors in the CMD PtIV transition state containing a higher coordination number than that occurring for related reactions in PdII catalysis that gives α-phenylation.

Item Details

Item Type:Refereed Article
Keywords:homogeneous catalysis, platinum catalysis, DFT, computational chemistry
Research Division:Chemical Sciences
Research Group:Other Chemical Sciences
Research Field:Organometallic Chemistry
Objective Division:Expanding Knowledge
Objective Group:Expanding Knowledge
Objective Field:Expanding Knowledge in the Chemical Sciences
Author:Canty, AJ (Professor Allan Canty)
Author:Ariafard, A (Associate Professor Alireza Ariafard)
ID Code:122448
Year Published:2017
Deposited By:Chemistry
Deposited On:2017-11-15
Last Modified:2017-11-15
Downloads:0

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