title: Synthesis of the pivalamidate-bridged pentanuclear platinum(II,III) linear complexes with Pt...Pt interactions.
abstract: Pentanuclear linear chain Pt(II,III) complexes [[Pt2(NH3)2X2((CH3)3CCONH)2(CH2COCH3)]2[PtX'4]].nCH3COCH3 (X = X' = Cl, n = 2 (1a), X = Cl, X' = Br, n = 1 (1b), X = Br, X' = Cl, n = 2 (1c), X = X' = Br, n = 1 (1d)) composed of a monomeric Pt(II) complex sandwiched by two amidate-bridged Pt dimers were synthesized from the reaction of the acetonyl dinuclear Pt(III) complexes having equatorial halide ligands [Pt2(NH3)2X2((CH3)3CCONH)2(CH2COCH3)]X' ' (X = Cl (2a), Br (2b), X' ' = NO3-, CH3C6H4SO3-, BF4-, PF6-, ClO4-), with K2[PtX'4] (X' = Cl, Br). The X-ray structures of 1a-1d show that the complexes have metal-metal bonded linear Pt5 structures, and the oxidation state of the metals is approximately Pt(III)-Pt(III)...Pt(II)...Pt(III)-Pt(III). The Pt...Pt interactions between the dimer units and the monomer are due to the induced Pt(II)-Pt(IV) polarization of the Pt(III) dimeric unit caused by the electron withdrawal of the equatorial halide ligands. The density functional theory calculation clearly shows that the Pt...Pt interactions between the dimers and the monomer are made by the electron transfer from the monomer to the dimers. The pentanuclear complexes have flexible Pt backbones with the Pt chain adopting either arch or sigmoid structures depending on the crystal packing.
authors.affiliation: Department of Chemistry, Advanced Research Center for Science and Engineering, Waseda University, 3-4-1 Okubo, Shinjuku-ku, Tokyo 169-8555, Japan. kmatsu@waseda.jp
authors.forename: Kazuko
authors.initials: K
authors.lastname: Matsumoto
authors.forename: Saiko
authors.initials: S
authors.lastname: Arai
authors.forename: Masahiko
authors.initials: M
authors.lastname: Ochiai
authors.forename: Wanzhi
authors.initials: W
authors.lastname: Chen
authors.forename: Ayako
authors.initials: A
authors.lastname: Nakata
authors.forename: Hiromi
authors.initials: H
authors.lastname: Nakai
authors.forename: Shuhei
authors.initials: S
authors.lastname: Kinoshita