Abstract
The new copper(I) complexes [Cu(L1)2](BF4), L1 = 2-pyridyl-N-(2'-methylthiophenyl)methyleneimine, and [Cu(L2)2](ClO4), L2 = 2-pyridyl-N-(2'-benzylthiophenyl)methyleneimine, were prepd. and structurally characterized. In contrast to the known [Cu(L1)2](ClO4)2, which exhibits partial thioether S binding to effect five-coordinate Cu2+, the copper(I) compds. reported here contain four-coordinate metal ions with exclusively N-donor binding. Cyclic voltammetry reveals a fully reversible oxidn. of the CuI species, which suggests a small barrier for reorganization. The redn. at neg. potentials is irreversible for compds. [Cu(L)2](X) and for the structurally characterized new compd. [Cu(L1)(PPh3)2](ClO4). UV/visible spectroelectrochem. shows the typical low-energy absorption bands of copper(I) (MLCT transition) and copper(II) (ligand-field transition) in the visible region; the CuII form develops an intense band at 350 nm attributed to a S-to-Cu ligand-to-metal charge transfer (LMCT). [on SciFinder(R)]
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