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Discovery and Mechanistic Investigation of Pt-Catalyzed Oxidative Homocoupling of Benzene with PhI(OAc)2

Abstract

We present a Pt-catalyzed direct coupling of benzene to biphenyl. This catalytic reaction employs the cyclometalated platinum(II) complex [PtMe(bhq)(SMe2)] (bhq = benzo[h]quinolate) with PhI(OAc)2 as oxidant and does not require an acid, a co-catalyst or a solvent. Reaction kinetics and characterization of potential catalytic species are reported. The reaction is first-order in Pt and second-order in benzene, which implicates the second C-H activation step as rate-determining. A Pt(II)/Pt(IV) catalytic cycle is suggested. The reaction commences by oxidation of the Pt(II) complex to give the platinum(IV) species [Pt(bhq)(SMe2)(OAc)2](OAc) followed by C-H activation of benzene to afford the intermediate [PtPh(bhq)(SMe2)(OAc)](OAc) concurrently with release of HOAc. A second benzene molecules reacts similarly to give the diphenyl intermediate [PtPh2(bhq)(SMe2)](OAc). C-C bond forming reductive elimination ensues to regenerate Pt(II) and complete catalytic cycle. The proposed mechanism has been examined by DFT computations, which provides support to experimental findings.

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Article information


Submitted
04 Nov 2019
Accepted
15 Jan 2020
First published
15 Jan 2020

Dalton Trans., 2020, Accepted Manuscript
Article type
Paper

Discovery and Mechanistic Investigation of Pt-Catalyzed Oxidative Homocoupling of Benzene with PhI(OAc)2

S. M. Nabavizadeh, F. Niroomand Hosseini, C. Park, G. Wu and M. M. Abu-Omar, Dalton Trans., 2020, Accepted Manuscript , DOI: 10.1039/C9DT04261J

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