Coordination of a Hemilabile N,N,S Donor Ligand in the Redox System CuL2+/2+, L = 2-Pyridyl-N-(2'-alkylthio-phenyl)methyleneimine

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European Journal of Inorganic Chemistry, (2011)
DOI: 10.1002/ejic.201001183


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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