title: A complete series of copper(II) halide complexes (X = F, Cl, Br, I) with a novel Cu(II)-C(sp3) bond.
abstract: A complete series of copper(ii) halide complexes [CuX(tptm)](X = F (), Cl (), Br (), I (); tptm = tris(2-pyridylthio)methyl) with a novel Cu(II)-C(sp(3)) bond has been prepared by the reactions of [Cu(tptm)(CH(3)CN)]PF(6)(.PF(6)) with corresponding halide sources of KF or n-Bu(4)NX (X = Cl, Br, I), and the trigonal bipyramidal structures have been confirmed by X-ray crystallography and/or EPR spectroscopy. The iodide complex easily liberates the iodide anion in acetonitrile forming the acetonitrile complex 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 Cu(II)/Cu(I) indicating a trigonal pyramidal coordination for Cu(I) 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.
authors.affiliation: Department of Molecular Materials Science, Graduate School of Science, Osaka City University, 3-3-138 Sugimoto, Sumiyoshi-ku, Osaka 558-8585, Japan.
authors.forename: Riichi
authors.initials: R
authors.lastname: Miyamoto
authors.forename: Ryoko
authors.initials: R
authors.lastname: Santo
authors.forename: Toshio
authors.initials: T
authors.lastname: Matsushita
authors.forename: Takanori
authors.initials: T
authors.lastname: Nishioka
authors.forename: Akio
authors.initials: A
authors.lastname: Ichimura
authors.forename: Yoshio
authors.initials: Y
authors.lastname: Teki
authors.forename: Isamu
authors.initials: I
authors.lastname: Kinoshita