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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:	https://doi.org/10.1039/c7dt03602g
Copyright Information:	Copyright 2017 The Royal Society of Chemistry
Related URLs:	UTAS Profile: Canty, AJ Google Scholar: Ariafard, A UTAS Profile: Ariafard, A
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