Computational study of selectivity in the [PtII Cl4 ]2- -catalysed arylation of arenes by diaryliodonium reagents: arene activation at PtIV centres

Dalton Transactions : an International Journal of Inorganic Chemistry
Allan J Canty, Alireza Ariafard

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.

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Citations

Jan 31, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·S Masoud NabavizadehMahdi M Abu-Omar

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