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

Allan J. Canty; Alireza Ariafard

doi:10.1039/c7dt03602g

Computational study of selectivity in the [Pt^IICl₄]^2--catalysed arylation of arenes by diaryliodonium reagents: Arene activation at Pt^IV centres

Allan J. Canty^*, Alireza Ariafard

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

4 Citations (Scopus)

Abstract

The mechanism for the [Pt^IICl₄]^2--catalysed reaction of Ph₂I^III(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 [Pt^IICl₄]^2-, giving trans-[PhPt^IVCl₄(TFA)]^2-. Transformation to cis-[PhPt^IVCl₃(TFA)]^- leads to reaction with NapH at the β-position in an inner-sphere Concerted Metalation Deprotonation (CMD) manner to give cis-[Ph(Nap)Pt^IVCl₃]^- and trifluoroacetic acid. Reductive elimination yields β-PhNap, and coordination of chloride regenerates [Pt^IICl₄]^2- for subsequent catalytic cycles. The selectivity for β-phenylation over α-phenylation is attributable to steric factors in the CMD Pt^IV transition state containing a higher coordination number than that occurring for related reactions in Pd^II catalysis that gives α-phenylation.

Original language	English
Pages (from-to)	15480-15486
Number of pages	7
Journal	Dalton Transactions
Volume	46
Issue number	44
DOIs	https://doi.org/10.1039/c7dt03602g
Publication status	Published - 2017
Externally published	Yes

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title = "Computational study of selectivity in the [PtIICl4]2--catalysed arylation of arenes by diaryliodonium reagents: Arene activation at PtIV centres",

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.",

author = "Canty, {Allan J.} and Alireza Ariafard",

note = "Publisher Copyright: {\textcopyright} 2017 The Royal Society of Chemistry.",

year = "2017",

doi = "10.1039/c7dt03602g",

language = "English",

volume = "46",

pages = "15480--15486",

journal = "Dalton Transactions",

issn = "1477-9226",

publisher = "Royal Society of Chemistry",

number = "44",

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TY - JOUR

T1 - Computational study of selectivity in the [PtIICl4]2--catalysed arylation of arenes by diaryliodonium reagents

T2 - Arene activation at PtIV centres

AU - Canty, Allan J.

AU - Ariafard, Alireza

PY - 2017

Y1 - 2017

N2 - 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.

AB - 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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U2 - 10.1039/c7dt03602g

DO - 10.1039/c7dt03602g

M3 - Article

C2 - 29090705

AN - SCOPUS:85034235754

SN - 1477-9226

VL - 46

SP - 15480

EP - 15486

JO - Dalton Transactions

JF - Dalton Transactions

IS - 44

ER -

Computational study of selectivity in the [Pt^IICl₄]^2--catalysed arylation of arenes by diaryliodonium reagents: Arene activation at Pt^IV centres

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