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

0358742 - ÚFCH JH 2012 RIV DE eng J - Journal Article
Schnödt, J. - Manzur, J. - García, A.-M. - Hartenbach, I. - Su, Ch. Y. - Fiedler, Jan - Kaim, W.
Coordination of a Hemilabile N,N,S Donor Ligand in the Redox System [CuL2](+/2+), L=2-Pyridyl-N-(2 '-alkylthiophenyl)methyleneimine.
European Journal of Inorganic Chemistry. -, č. 9 (2011), s. 1436-1441. ISSN 1434-1948. E-ISSN 1099-0682
R&D Projects: GA ČR GA203/09/0705; GA MŠMT(CZ) LD11082
Institutional research plan: CEZ:AV0Z40400503
Keywords : copper * diimines * ligand effects
Subject RIV: CF - Physical ; Theoretical Chemistry
Impact factor: 3.049, year: 2011

The new copper(I) complexes [Cu(L-1)(2)](BF4), L-1 = 2-pyridyl-N-(2'-methylthiophenyl)methyleneimine, and [Cu(L-2)(2)](ClO4), L-2 = 2-pyridyl-N-(2'-benzylthiophenyl)methyleneimine, have been prepared and structurally characterized. In contrast to the known [Cu(L-1)(2)](ClO4)(2), which exhibits partial thioether S binding to effect five-coordinate Cu2+, the copper(I) compounds reported here contain four-coordinate metal ions with exclusively N-donor binding. Cyclic voltammetry reveals a fully reversible oxidation of the Cu-I species, which suggests a small barrier for reorganization. The reduction at negative potentials is irreversible for compounds [Cu(L)(2)](X) and for the structurally characterized new compound [Cu(L-1)(PPh3)(2)](ClO4). UV/Vis spectroelectrochemistry shows the typical low-energy absorption bands of copper(I) (MLCT transition) and copper(II) (ligand-field transition) in the visible region.
Permanent Link: http://hdl.handle.net/11104/0196688