Synthesis, molecular and electronic structure of the first homoleptic complex of platinum with a secondary phosphine
Synthesis, molecular and electronic structure of the first homoleptic complex of platinum with a secondary phosphine
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铂与仲膦第一个均配配合物的合成、分子和电子结构
DOI：
10.1016/s0020-1693(97)05679-x
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发表时间：
1997
影响因子：
2.8
通讯作者：
G. Germano
中科院分区：
文献类型：
--
作者：
P. Leoni;Giuseppina Chiaradonna;M. Pasquali;F. Marchetti;A. Fortunelli;G. Germano
CpPt(η_3-C_3H_5)与PBu12H在丙酮中反应，得到了铂(0)单核衍生物PT(PBu12H)_3(1)。变温31P1H核磁共振谱表明，化合物1在甲苯溶液中解离了其中一个膦，生成了14E−铂(PBuP12H)2。用X-射线衍射法测定了化合物1的晶体和分子结构，结果表明，膦分子呈三角平面排列(C24H57P3PT：六方，空间群P63/m，a=b=10.4150(11)，c=16.263(3)Å，Z=2)。在傅里叶变换图中，P--H氢原子位于配位平面内，叔丁基取代基呈遮蔽构型。从头算和分子动力学计算基本证实了X-射线衍射法得到的结构。排除了无空间的铂--H--P相互作用，并用空间相互作用解释了几何构型。
The reaction of CpPt(η3-C3H5) with PBu12H in acetone gives the Pt(0) mononuclear derivative Pt(PBu12H)3(1). As demonstrated by variable temperature31P1H NMR spectra, complex 1 dissociates one of the phosphines in toluene solution affording the 14e−Pt(PBuP12H)2. The crystal and molecular structure of 1 was solved by X-ray diffraction which reveals a trigonal planar disposition of the phosphine molecules (C24H57P3Pt: hexagonal, space group P63/m, a = b = 10.4150(11), c = 16.263(3) A ̊ , Z = 2 ). The PH hydrogen atoms were located in the Fourier map and were found to lie in the coordination plane, with the t-butyl substituents in an eclipsed configuration. Ab initio and molecular dynamics calculations essentially confirm the structure obtained by X-ray diffraction. An agostic PtHP interaction was excluded and the geometry was explained in terms of steric interactions.