Non-innocent ligand behaviour of a bimetallic Cu complex employing a bridging catecholate

Dalton Transactions : an International Journal of Inorganic Chemistry
Tim J DunnTim Storr

Abstract

The geometric and electronic structure of a bimetallic Cu Schiff-base complex and its one-electron oxidized form have been investigated. The two salen units in the neutral complex 1 are linked via a bridging catecholate function, and the coupling between the two Cu(II) d(9) centres was determined to be weakly antiferromagnetic on the basis of solid-state magnetic studies (J = -3 cm(-1)), and variable-temperature electron paramagnetic resonance (EPR) (J = -3 cm(-1)). Theoretical calculations (DFT) were in agreement with the experimental results (J = -7 cm(-1)), and provided insight into the coupling mechanism for the neutral system. One-electron oxidation provided [1](+) which was observed to have limited stability in solution. The oxidized complex was determined to be a ligand radical species in solution, with the electron hole potentially localized on the redox-active dioxolene, the phenolate ligands, or delocalized over the entire ligand system. Electrochemical experiments and UV-vis-NIR spectroscopy, in combination with density functional theory (DFT) calculations, provided insight into the locus of oxidation and the degree of delocalization in this system. The ligand radical for [1˙](+) was determined experimentally to be l...Continue Reading

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