Department of Molecular Materials Science, Graduate School of Science, Osaka City University, 3-3-138 Sugimoto, Sumiyoshi-ku, Japan
E-mail: firstname.lastname@example.org; Fax: +81 6 6690 2753
; Tel: +81 6 6605 2546
Dalton Trans., 2005, 3179-3186
19 May 2005,
20 Jul 2005
First published online
15 Aug 2005
A complete series of copper(II) halide complexes [CuX(tptm)]
(X = F (1), Cl (2), Br (3), I (4); tptm = tris(2-pyridylthio)methyl) with a novel CuII–C(sp3) bond has been prepared by the reactions of [Cu(tptm)(CH3CN)]PF6
(5·PF6) with corresponding halide sources of KF or n-Bu4NX (X = Cl, Br, I), and the trigonal bipyramidal structures have been confirmed by X-ray crystallography and/or EPR spectroscopy. The iodide complex 4 easily liberates the iodide anion in acetonitrile forming the acetonitrile complex 5 as a result. The EPR spectra of the complexes showed several superhyperfine structures that strongly indicated the presence of spin density on the halide ligands through the Cu–X bond. The results of DFT calculations essentially matched with the X-ray crystallographic and the EPR spectroscopic results. Cyclic voltammetry revealed a quasi-reversible reduction wave for CuII/CuI indicating a trigonal pyramidal coordination for CuI states. A coincidence of the redox potential for all [CuX(tptm)]0/+ processes indicates that the main oxidation site in each complex is the tptm ligand.
Fetching data from CrossRef. This may take some time to load.