Recent Advances in Metal-Mediated Carbon-Carbon Bond Cleavages of Benzenoid Hydrocarbons

Abstract

A variety of metal coordination modes that may provide carbon-carbon bond cleavage pathways in benzene and benzenoid hydrocarbons are summarized in a rubric. Some of these are evident in recently published work, and others represent challenges for future research. The first category includes thermolyses and ring opening metathesis polymerization of iridium η⁴ adducts, aluminum(I) additions that first yield η² 1,2- or 1,4 adducts, intramolecular C=C metatheses that involve initial 1,2 Mo=C additions, multimetallic activation via dititanium η³ binding modes, and a one-off lutetium mediated process that defies simple classification. However, few of these transformations are currently catalytic. The interpretation of most has been aided by DFT calculations, and related lines of investigation are briefly treated.

Keywords

C=C metathesis / Benzene activation / Büchner reaction / Metalla(norcaradiene) / Benzene ligands

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2025 The Author(s). Chinese Journal of Chemistry published by SIOC, CAS, Shanghai and Wiley-VCH GmbH