EPR study of intramolecular dynamics in o-semiquinonic nickel complexes with PCP-pincer ligand in solution

A number of square pyramidal o-semiquinonic nickel complexes with 2,6-bis(diphenylphosphinomethyl)phenyl were investigated by EPR spectroscopy in solution. The complexes have flexible coordination spheres and can exist in solution as two isomers rapidly (on the EPR timescale) interconverting one to...

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Published in:Dalton transactions : an international journal of inorganic chemistry 2004-09 (18), p.2957-2962
Main Authors: Kozhanov, Konstantin A, Bubnov, Michael P, Cherkasov, Vladimir K, Fukin, Georgy K, Abakumov, Gleb A
Format: Article
Language:English
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Summary:A number of square pyramidal o-semiquinonic nickel complexes with 2,6-bis(diphenylphosphinomethyl)phenyl were investigated by EPR spectroscopy in solution. The complexes have flexible coordination spheres and can exist in solution as two isomers rapidly (on the EPR timescale) interconverting one to another at room temperature. The equilibrium is entropy driven and does not significantly depend on the substituents in the semiquinone ring. The spin density distribution depends on mesomeric properties and bulkiness of substituents in ortho-position to oxygen atoms.
ISSN:1477-9226
1477-9234
DOI:10.1039/B407972H