195Pt NMR spectra of head-to-head and head-to-tail amidato-bridged platinum(III) dinuclear complexes

Satoshi Iwatsuki, Eigo Isomura, Atsushi Wada, Koji Ishihara, Kazuko Matsumoto

    Research output: Contribution to journalArticle

    3 Citations (Scopus)

    Abstract

    195Pt Chemical shifts and 1JPt-Pt coupling constants were measured for a series of head-to-head (HH) and head-to-tail (HT) amidato-bridged cis-diammineplatinum(III) dinuclear complexes involved in the axial water substitution reactions with halide ions (X- = Cl -, Br-): HH-[Pt2(NH3) 4(μ-amidato)2L1L2]n+ ≡ [L1-Pt(N2O2)-Pt(N4)-L 2]n+ (amidato = α-pyridonato, α-pyrrolidonato, and pivalamidato) and HT-[Pt2(NH3)4(μ- α-pyridonato)2L1L2]n+ ≡ [L1-Pt(N3O)-Pt(N3O)-L2] n+; the diaqua (L1, L2 = H2O, n = 4), the aquahalo (L1 = X-, L2 = H2O, n = 3), and the dihalo complexes (L1, L2 = X-, n = 2). The 195Pt NMR spectroscopic data were considered in relation to the lability in the axial ligand substitution reaction and the electron distribution along the Pt-Pt bond. The NMR spectroscopic data suggested different electron distributions along the Pt-Pt bonds in all the HH dimers and in the HT aquahalo dimers, such as [L1-PtIV(N 2O2)-PtII(N4)-L2] n+ and [X-PtIV(N3O)-PtII-(N 3O)-OH2]3+, respectively. Relative shifts of the 195Pt NMR signals for each substitution step indicate that the replacement of the axial water ligand by X- affects more effectively the electron density of the opposite Pt atom than that of the substituted one.

    Original languageEnglish
    Pages (from-to)2484-2490
    Number of pages7
    JournalEuropean Journal of Inorganic Chemistry
    Issue number12
    DOIs
    Publication statusPublished - 2006 Jun 19

    Fingerprint

    Platinum
    Substitution reactions
    Nuclear magnetic resonance
    Dimers
    Ligands
    Electrons
    Water
    Chemical shift
    Carrier concentration
    Ions
    Atoms

    Keywords

    • α-Pyridone
    • α-Pyrrolidone
    • NMR spectroscopy
    • Pivalamide
    • Platinum Pt NMR

    ASJC Scopus subject areas

    • Inorganic Chemistry

    Cite this

    195Pt NMR spectra of head-to-head and head-to-tail amidato-bridged platinum(III) dinuclear complexes. / Iwatsuki, Satoshi; Isomura, Eigo; Wada, Atsushi; Ishihara, Koji; Matsumoto, Kazuko.

    In: European Journal of Inorganic Chemistry, No. 12, 19.06.2006, p. 2484-2490.

    Research output: Contribution to journalArticle

    Iwatsuki, Satoshi ; Isomura, Eigo ; Wada, Atsushi ; Ishihara, Koji ; Matsumoto, Kazuko. / 195Pt NMR spectra of head-to-head and head-to-tail amidato-bridged platinum(III) dinuclear complexes. In: European Journal of Inorganic Chemistry. 2006 ; No. 12. pp. 2484-2490.
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    abstract = "195Pt Chemical shifts and 1JPt-Pt coupling constants were measured for a series of head-to-head (HH) and head-to-tail (HT) amidato-bridged cis-diammineplatinum(III) dinuclear complexes involved in the axial water substitution reactions with halide ions (X- = Cl -, Br-): HH-[Pt2(NH3) 4(μ-amidato)2L1L2]n+ ≡ [L1-Pt(N2O2)-Pt(N4)-L 2]n+ (amidato = α-pyridonato, α-pyrrolidonato, and pivalamidato) and HT-[Pt2(NH3)4(μ- α-pyridonato)2L1L2]n+ ≡ [L1-Pt(N3O)-Pt(N3O)-L2] n+; the diaqua (L1, L2 = H2O, n = 4), the aquahalo (L1 = X-, L2 = H2O, n = 3), and the dihalo complexes (L1, L2 = X-, n = 2). The 195Pt NMR spectroscopic data were considered in relation to the lability in the axial ligand substitution reaction and the electron distribution along the Pt-Pt bond. The NMR spectroscopic data suggested different electron distributions along the Pt-Pt bonds in all the HH dimers and in the HT aquahalo dimers, such as [L1-PtIV(N 2O2)-PtII(N4)-L2] n+ and [X-PtIV(N3O)-PtII-(N 3O)-OH2]3+, respectively. Relative shifts of the 195Pt NMR signals for each substitution step indicate that the replacement of the axial water ligand by X- affects more effectively the electron density of the opposite Pt atom than that of the substituted one.",
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    T1 - 195Pt NMR spectra of head-to-head and head-to-tail amidato-bridged platinum(III) dinuclear complexes

    AU - Iwatsuki, Satoshi

    AU - Isomura, Eigo

    AU - Wada, Atsushi

    AU - Ishihara, Koji

    AU - Matsumoto, Kazuko

    PY - 2006/6/19

    Y1 - 2006/6/19

    N2 - 195Pt Chemical shifts and 1JPt-Pt coupling constants were measured for a series of head-to-head (HH) and head-to-tail (HT) amidato-bridged cis-diammineplatinum(III) dinuclear complexes involved in the axial water substitution reactions with halide ions (X- = Cl -, Br-): HH-[Pt2(NH3) 4(μ-amidato)2L1L2]n+ ≡ [L1-Pt(N2O2)-Pt(N4)-L 2]n+ (amidato = α-pyridonato, α-pyrrolidonato, and pivalamidato) and HT-[Pt2(NH3)4(μ- α-pyridonato)2L1L2]n+ ≡ [L1-Pt(N3O)-Pt(N3O)-L2] n+; the diaqua (L1, L2 = H2O, n = 4), the aquahalo (L1 = X-, L2 = H2O, n = 3), and the dihalo complexes (L1, L2 = X-, n = 2). The 195Pt NMR spectroscopic data were considered in relation to the lability in the axial ligand substitution reaction and the electron distribution along the Pt-Pt bond. The NMR spectroscopic data suggested different electron distributions along the Pt-Pt bonds in all the HH dimers and in the HT aquahalo dimers, such as [L1-PtIV(N 2O2)-PtII(N4)-L2] n+ and [X-PtIV(N3O)-PtII-(N 3O)-OH2]3+, respectively. Relative shifts of the 195Pt NMR signals for each substitution step indicate that the replacement of the axial water ligand by X- affects more effectively the electron density of the opposite Pt atom than that of the substituted one.

    AB - 195Pt Chemical shifts and 1JPt-Pt coupling constants were measured for a series of head-to-head (HH) and head-to-tail (HT) amidato-bridged cis-diammineplatinum(III) dinuclear complexes involved in the axial water substitution reactions with halide ions (X- = Cl -, Br-): HH-[Pt2(NH3) 4(μ-amidato)2L1L2]n+ ≡ [L1-Pt(N2O2)-Pt(N4)-L 2]n+ (amidato = α-pyridonato, α-pyrrolidonato, and pivalamidato) and HT-[Pt2(NH3)4(μ- α-pyridonato)2L1L2]n+ ≡ [L1-Pt(N3O)-Pt(N3O)-L2] n+; the diaqua (L1, L2 = H2O, n = 4), the aquahalo (L1 = X-, L2 = H2O, n = 3), and the dihalo complexes (L1, L2 = X-, n = 2). The 195Pt NMR spectroscopic data were considered in relation to the lability in the axial ligand substitution reaction and the electron distribution along the Pt-Pt bond. The NMR spectroscopic data suggested different electron distributions along the Pt-Pt bonds in all the HH dimers and in the HT aquahalo dimers, such as [L1-PtIV(N 2O2)-PtII(N4)-L2] n+ and [X-PtIV(N3O)-PtII-(N 3O)-OH2]3+, respectively. Relative shifts of the 195Pt NMR signals for each substitution step indicate that the replacement of the axial water ligand by X- affects more effectively the electron density of the opposite Pt atom than that of the substituted one.

    KW - α-Pyridone

    KW - α-Pyrrolidone

    KW - NMR spectroscopy

    KW - Pivalamide

    KW - Platinum Pt NMR

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