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

*この研究の対応する著者

研究成果: Article査読

26 被引用数 (Scopus)

抄録

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.

本文言語English
ページ(範囲)8552-8560
ページ数9
ジャーナルInorganic Chemistry
44
23
DOI
出版ステータスPublished - 2005 11 14

ASJC Scopus subject areas

  • 物理化学および理論化学
  • 無機化学

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