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Ligand Redox Non‐Innocence in Transition‐Metal σ‐Alkynyl and Related Complexes
Author(s) -
Schauer Phil A.,
Low Paul J.
Publication year - 2012
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201100995
Subject(s) - chemistry , transition metal , ligand (biochemistry) , redox , reagent , metal , radical , non innocent ligand , combinatorial chemistry , electron transfer , photochemistry , molecular electronics , inorganic chemistry , molecule , organic chemistry , catalysis , biochemistry , receptor
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.