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首页> 外文期刊>Zeitschrift fur Anorganische und Allgemeine Chemie >Structure and bonding of the mixed-valent platinum trihalides, PtCl3 and PtBr3
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Structure and bonding of the mixed-valent platinum trihalides, PtCl3 and PtBr3

机译：混合价三卤化铂PtCl3和PtBr3的结构和键合

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摘要

The isotypical crystal structures of the mixed valent trihalides PtCl3 and PtBr3 were redetermined by single crystal methods (space group R (3) over bar, trigonal setting; PtCl3: a = 21.213 Angstrom, c = 8.600 Angstrom, cla = 0.4054; Z = 36: 1719 hkl; R = 0.035; PtBr3: a = 22.318 Angstrom. c = 9.034 Angstrom; cla = 0.4048; Z = 36; 1606 hkl; R = 0.027). A cubic closest packing of X- anions forms the basis of an optimized arrangement of cuboctahedrally [Pt6X12] cluster molecules with Pt-II and enantiomers of helical chains of edge-condensed [PtX2X4/2] octahedra with Pt-IV in cis-Delta- and cis-Lambda-configuration, respectively The bond lengths vary with the function of the X- ligands ((d) over bar (Pt-II-X) = 2.315 and 2.445 Angstrom; (d) over bar (Pt-II-Pt-II) = 3.336 and 3.492 Angstrom; d(Pt-IV-X) = 2.286 - 2.417 Angstrom and 2.437 - 2.563 Angstrom). The P-II atoms are shifted outwards the X-12 cuboctahedra by 0.045 Angstrom and 0.024 Angstrom, respectively. The symmetry governed Periodic Nodal Surface, PNS, perfectly separates the regions of different valencies. Quantum chemical calculations exclude the possible additional interactions between P-II and one of the exo-ligands of Pt-IV.
机译：混合价三卤化物PtCl3和PtBr3的同型晶体结构通过单晶方法重新确定（空间组R（3）在bar，三角背景上; PtCl3：a = 21.213埃，c = 8.600埃，cla = 0.4054; Z = 36 ：1719hkl; R ＝ 0.035; PtBr 3：a ＝ 22.318埃; c ＝ 9.034埃; cla ＝ 0.4048; Z ＝ 36; 1606hkl; R ＝ 0.027）。 X阴离子的立方最紧密堆积形成了具有Pt-II的立方八面体[Pt6X12]簇分子和边缘缩合的[PtX2X4 / 2]八面体与Pt-IV的螺旋链对映异构体的最佳排列的基础，顺式Delta-键长随X-配体的作用而变化（（d）超过bar（Pt-II-X）= 2.315和2.445埃;（d）超过bar（Pt-II-Pt -II）＝ 3.336和3.492埃; d（Pt-IV-X）＝ 2.286-2.417埃和2.437-2.563埃。 P-II原子分别向外移动X-12八面体0.045埃和0.024埃。对称控制的周期性节点面PNS完美地分隔了不同价态的区域。量子化学计算排除了P-II与Pt-IV的外泌配体之间可能存在的其他相互作用。

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