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首页> 外文期刊>Polyhedron: The International Journal for Inorganic and Organometallic Chemistry >Structural and spectroscopic characterization of silver(I) tribenzylphosphane complexes including chloro and bromo derivatives with unusual stoichiometries and an iodo complex with a Ag_(13)I_(13) cluster core
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Structural and spectroscopic characterization of silver(I) tribenzylphosphane complexes including chloro and bromo derivatives with unusual stoichiometries and an iodo complex with a Ag_(13)I_(13) cluster core

机译：银（I）三苄基膦配合物的结构和光谱表征，包括具有异常化学计量比的氯和溴衍生物，以及具有Ag_（13）I_（13）簇核的碘配合物

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摘要

The reaction of tribenzylphosphane (PBn_3) with silver(I) halides, AgX (X = Cl, Br and I), afforded the cluster compound, [Ag _(13)I_(13)(PBn_3)_6 ] (1), a low-yielding ionic salt, [Ag(PBn_3)_2]_8[AgCl _3]Cl_6·6H_2O (2), and a non-stoichiometric compound, Ag～_(11.5)Br～_(11.5)(PBn_3) _(16)·～5.5H_2O (3). As well, reactions with the appropriate Ag salt and PBn_3 in a 1:2 M ratio yielded [Ag(PBn _3)_2]PF_6 (4), [Ag(PBn_3) _2]BF_4 (5) and [Ag(PBn_3)_2Cl] ·0.33CHCl_3 (6) while [Ag(PBn_3)_2I] (7) was obtained when the ratio was 4:1. The iodo-cluster 1 has an onion-like structure with an iodide ion at its center surrounded trigonal-prismatically by an inner core of six silver ions. These silver ions are tetrahedrally coordinated to the innermost iodide ion and by six iodides that bridge to an outer layer of six silver ions which themselves are tetrahedrally coordinated by six bridging iodides and capped by the six PBn3 ligands. The top of the onion features a silver ion with three iodo ligands arranged in a near-planar trigonal arrangement around it. Single crystal X-ray crystallography shows the complexes 2 and 3 to contain columns of discrete [Ag(PBn _3)_2]~+ cations with a linear P-Ag-P coordination, as also observed in the simple salts, 4 and 5, where the anion is [PF6]- and [BF_4]~-. The phenyl groups of PBn_3 swing back over the silver to generate a sixfold phenyl embrace. However, in 3, although the PBn_3 sites are fully occupied, about a quarter of the sixfold phenyl embraces are devoid of the object of their attention, the encapsulated silver ion. For 2, the [AgCl_3] ~(2-) anions are trigonal-planar, three-coordinated. For 3, the AgBr32-appear as motifs in an approximately 25% silver-deficient Ag _4Br62-cluster. The crystal structures of the three-coordinate halides, 6 and 7, show that the geometry around the silver is close to a T-shape, with the chloride and iodide ions bound. The far-IR and ~(31)P CP MAS NMR spectra of a selection of the new complexes confirm aspects of their symmetry as deduced from the crystallographic studies.
机译：三苄基膦（PBn_3）与卤化银（I）AgX（X = Cl，Br和I）反应，得到簇化合物[Ag _（13）I_（13）（PBn_3）_6]（1），低产率离子盐[Ag（PBn_3）_2] _8 [AgCl _3] Cl_6·6H_2O（2）和非化学计量化合物Ag〜_（（11.5）Br〜_（11.5）（PBn_3）_（16） ）·〜5.5H_2O（3）。同样，与适当的Ag盐和PBn_3以1：2 M的比例反应生成[Ag（PBn _3）_2] PF_6（4），[Ag（PBn_3）_2] BF_4（5）和[Ag（PBn_3）_2Cl ]·0.33CHCl_3（6）而[Ag（PBn_3）_2I]（7）的比例为4：1时。碘簇1具有洋葱状的结构，在其中心具有由六个银离子的内心三角形包围的碘离子。这些银离子被四面体配位到最里面的碘离子，并被六个碘化物桥连到六个银离子的外层，而六个银离子本身被六个桥联碘化物四面配位并被六个PBn3配体封端。洋葱的顶部是一个银离子，周围有三个碘配体，它们以近似平面的三角形排列。单晶X射线晶体学显示配合物2和3包含具有线性P-Ag-P配位的离散[Ag（PBn _3）_2]〜+阳离子列，在简单的盐4和5中也观察到阴离子为[PF6]-和[BF_4]〜-。 PBn_3的苯基在银上向后摆动，以产生六倍的苯基包围。然而，在3中，尽管PBn_3位点被完全占据，但是大约六分之六的苯基环抱没有引起人们注意的目的，即封装的银离子。对于2，[AgCl_3]〜（2-）阴离子是三角平面的，三配位的。对于3，在约25％的缺银Ag _4Br62簇中，AgBr32作为图案出现。三配位卤化物6和7的晶体结构表明，银周围的几何形状接近T形，结合了氯离子和碘离子。选择的新配合物的远红外和〜（31）P CP MAS NMR光谱证实了根据晶体学研究推导的对称性。

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