Ligand Redox Non-Innocence in Transition-Metal σ-Alkynyl and Related Complexes

P.A. Schauer, Paul Low

Research output: Contribution to journalReview article

61 Citations (Scopus)


Transition-metal σ-alkynyl complexes are valuable functional materials that have found application as sructural units in the assembly of polymetallic arrays and large molecular structures, reagents for the transfer, oligomerisation or functionalisation of alkynes, magnetic or optical materials and putative components for use in a future molecular-based electronics platform. Many σ-alkynyl complexes are redox-active, undergoing facile oxidation (reduction) at moderate potentials to generate radical cations (anions) in which the charge and spin density can be tuned from being largely metal-centred to alkynyl ligand-centred by variation of the nature of the metal, supporting ligands and alkynyl substituents. This review summarises the diverse chemical behaviour of metal-supported σ-alkynyl radicals, and some selected closely related systems, which can often be rationalised in terms of the distribution of electron-spin density over the metal–alkynyl scaffold.
Original languageEnglish
Pages (from-to)390 - 411
JournalEuropean Journal of Inorganic Chemistry
Issue number3
Early online date13 Dec 2011
Publication statusPublished - Jan 2012


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