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Computational study of selectivity in the [PtIICl4]2−-catalysed arylation of arenes by diaryliodonium reagents: arene activation at PtIV centres
journal contribution
posted on 2023-05-19, 13:30 authored by Allan CantyAllan Canty, Alireza AriafardAlireza AriafardThe 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.
History
Publication title
Dalton TransactionsVolume
46Pagination
15480-15486ISSN
1477-9226Department/School
School of Natural SciencesPublisher
Royal Soc ChemistryPlace of publication
Thomas Graham House, Science Park, Milton Rd, Cambridge, England, Cambs, Cb4 0WfRights statement
Copyright 2017 The Royal Society of ChemistryRepository Status
- Restricted