Abstract
The redox chemistry and e.s.r. spectra of a number of copper(II) complexes with nitrogen- and sulphur-donor ligands have been examined, including complexes with 2,2′-bi-imidazole, histamine, and cyclic and acyclic saturated amine and thioether ligands. The tetrahedral CuIIS4 centre generated by γ-irradiation of single crystals of a thioacetamide complex of CuI has a low value of |A∥|. Tetrahedral distortion of otherwise tetragonal copper(II) centres increases g∥ and decreases |A∥| for N-, S-, and O-donor ligands, and is a more effective source of reduction of |A∥| than charge effects. The quotient g∥/|A∥| appears to be a convenient empirical index of distortion of the donor set from planar toward tetrahedral, indicating that most type I copper in proteins is tetrahedrally, rather than tetragonally, co-ordinated.
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