Synthesis of the pivalamidate-bridged pentanuclear platinum(II,III) linear complexes with Pt⋯Pt interactions

Kazuko Matsumoto, Saiko Arai, Masahiko Ochiai, Wanzhi Chen, Ayako Nakata, Hiromi Nakai, Shuhei Kinoshita

Research output: Contribution to journalArticle

27 Citations (Scopus)

Abstract

Pentanuclear linear chain Pt(II,III) complexes {[Pt2(NH 3)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 [Pt 2(NH3)2X2((CH3) 3CCONH)2-(CH2COCH3)]X″ (X = Cl (2a), Br (2b), X″ = NO3-, CH3C 6H4SO3-, BF4-, PF6-, ClO4-), with K 2[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.

Original languageEnglish
Pages (from-to)8552-8560
Number of pages9
JournalInorganic Chemistry
Volume44
Issue number23
DOIs
Publication statusPublished - 2005 Nov 14

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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