Selective cleavage of unactivated arene ring C-C bonds by iridium: key roles of benzylic C-H activation and metal-metal cooperativity

Tian, Yancong ORCID: 0000-0001-9075-0363, Jakoobi, Martin, Boulatov, Roman ORCID: 0000-0002-7601-4279 and Sergeev, Alexey G ORCID: 0000-0003-1587-2517 (2021) Selective cleavage of unactivated arene ring C-C bonds by iridium: key roles of benzylic C-H activation and metal-metal cooperativity. CHEMICAL SCIENCE, 12 (10). pp. 3568-3579.

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Official URL: http://dx.doi.org/10.1039/d0sc05900e

Abstract

The cleavage of aromatic C-C bonds is central for conversion of fossil fuels into industrial chemicals and designing novel arene functionalisations through ring opening, expansion and contraction. However, the current progress is hampered by both the lack of experimental examples of selective oxidative addition of aromatic C-C bonds and limited understanding of the factors that favour insertion into the C-C rather than the C-H bonds. Here, we describe the comprehensive mechanism of the only reported chemo- and regioselective insertion of a transition metal into a range of substituted arene rings in simple iridium(i) complexes. The experimental and computational data reveal that this ring cleavage requires both reversible scission of a benzylic C-H bond and cooperativity of two Ir centres sandwiching the arene in the product-determining intermediate. The mechanism explains the chemoselectivity and scope of this unique C-C activation in industrially important methylarenes and provides a general insight into the role of metal-metal cooperativity in the cleavage of unsaturated C-C bonds.

Item Type:	Article
Depositing User:	Symplectic Admin
Date Deposited:	13 Jan 2021 09:44
Last Modified:	18 Jan 2023 23:03
DOI:	10.1039/d0sc05900e
Related URLs:	Author Publisher
URI:	https://livrepository.liverpool.ac.uk/id/eprint/3113389