TY - JOUR
T1 - Synthesis of the pivalamidate-bridged pentanuclear platinum(II,III) linear complexes with Pt⋯Pt interactions
AU - Matsumoto, Kazuko
AU - Arai, Saiko
AU - Ochiai, Masahiko
AU - Chen, Wanzhi
AU - Nakata, Ayako
AU - Nakai, Hiromi
AU - Kinoshita, Shuhei
PY - 2005/11/14
Y1 - 2005/11/14
N2 - 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.
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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U2 - 10.1021/ic050942a
DO - 10.1021/ic050942a
M3 - Article
C2 - 16270995
AN - SCOPUS:28244502180
SN - 0020-1669
VL - 44
SP - 8552
EP - 8560
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 23
ER -