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

Canty, AJ and Ariafard, A ORCID: 0000-0003-2383-6380 2017 , 'Computational study of selectivity in the [PtIICl4]2−-catalysed arylation of arenes by diaryliodonium reagents: arene activation at PtIV centres' , Dalton Transactions, vol. 46 , pp. 15480-15486 , doi: 10.1039/c7dt03602g.

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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 Type: Article
Authors/Creators:Canty, AJ and Ariafard, A
Keywords: homogeneous catalysis, platinum catalysis, DFT, computational chemistry
Journal or Publication Title: Dalton Transactions
Publisher: Royal Soc Chemistry
ISSN: 1477-9226
DOI / ID Number: 10.1039/c7dt03602g
Copyright Information:

Copyright 2017 The Royal Society of Chemistry

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