Synthesis of the pivalamidate-bridged pentanuclear platinum(II,III) linear complexes with Pt•••Pt interactions
Synthesis of the pivalamidate-bridged pentanuclear platinum(II,III) linear complexes with Pt•••Pt interactions
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DOI：
10.1021/ic050942a
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发表时间：
2005-11-14
影响因子：
4.6
通讯作者：
Kinoshita, S
中科院分区：
文献类型：
--
作者：
Matsumoto, K;Arai, S;Kinoshita, S
五环的线性链Pt (II, III)复合物{[第2部分(NH3) (2) X - 2 ((CH3) (3) CCONH) (2) (CH2COCH3) (2) (PtX(4)]}中心圆点nCH (3) COCH (3) (X = X”= Cl, n = 2 (1), X = Cl, X = Br, n = 1 (1 b), X = Br, X”= Cl, n = 2 (1 c), X = X ' = Br, n = 1 (1 d))组成的单体的Pt(2)复杂的夹在两个amidate-bridged Pt二聚体合成反应的丙酮基双核的Pt (III)复合物在赤道卤化物配体(第2部分(NH3) (2) X - 2 ((CH3) (3) CCONH) (2) - (CH2COCH3) X (X = Cl (2),Br (2 b), X = NO3 CH3C6H4SO3、BF4, PF6 - ClO4),与K-2 (PtX (4)] (X ' = Cl, Br)。x射线结构表明配合物具有金属-金属键合的线性Pt-5结构，金属的氧化态近似为Pt(III)-Pt（III）中心点中心点中心点Pt（II）中心点中心点中心点Pt(III)-Pt（III）。二聚体单元与单体之间的Pt中心点中心点中心点Pt相互作用是由于赤道卤化物配体的电子撤回引起Pt（III）二聚体单元的Pt(II)-Pt（IV）极化引起的。密度泛函理论计算清楚地表明，二聚体与单体之间的Pt中心点中心点中心点Pt相互作用是通过电子从单体向二聚体的转移来实现的。五核配合物具有灵活的Pt骨架，根据不同的晶体排列，Pt链采用拱形或s形结构。
Pentanuclear linear chain Pt(II,III) complexes {[Pt-2(NH3)(2)X-2((CH3)(3)CCONH)(2)(CH2COCH3)](2)[PtX'(4)]}center dot nCH(3)COCH(3) (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)(2)X-2((CH3)(3)CCONH)(2)-(CH2COCH3)]X" (X = Cl (2a), Br (2b), X" = NO3-, CH3C6H4SO3-, 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 Pt-5 structures, and the oxidation state of the metals is approximately Pt(III)-Pt(III)center dot center dot center dot Pt(II)center dot center dot center dot Pt(III)-Pt(III). The Pt center dot center dot center dot 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 center dot center dot center dot 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.