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

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    Platinum
    Dimers
    platinum
    dimers
    monomers
    Monomers
    synthesis
    halides
    Metals
    interactions
    metals
    Ligands
    ligands
    arches
    Electrons
    Arches
    Metal complexes
    Density functional theory
    electron transfer
    Polarization

    ASJC Scopus subject areas

    • Inorganic Chemistry

    Cite this

    Synthesis of the pivalamidate-bridged pentanuclear platinum(II,III) linear complexes with Pt⋯Pt interactions. / Matsumoto, Kazuko; Arai, Saiko; Ochiai, Masahiko; Chen, Wanzhi; Nakata, Ayako; Nakai, Hiromi; Kinoshita, Shuhei.

    In: Inorganic Chemistry, Vol. 44, No. 23, 14.11.2005, p. 8552-8560.

    Research output: Contribution to journalArticle

    Matsumoto, Kazuko ; Arai, Saiko ; Ochiai, Masahiko ; Chen, Wanzhi ; Nakata, Ayako ; Nakai, Hiromi ; Kinoshita, Shuhei. / Synthesis of the pivalamidate-bridged pentanuclear platinum(II,III) linear complexes with Pt⋯Pt interactions. In: Inorganic Chemistry. 2005 ; Vol. 44, No. 23. pp. 8552-8560.
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    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.",
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    AU - Matsumoto, Kazuko

    AU - Arai, Saiko

    AU - Ochiai, Masahiko

    AU - Chen, Wanzhi

    AU - Nakata, Ayako

    AU - Nakai, Hiromi

    AU - Kinoshita, Shuhei

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    AB - 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.

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