Pyridine-2-thione (pySH) derivatives of silver(I): Synthesis and crystal structures of dinuclear [Ag2Cl2(mu-S-pySH)(2)(PPh3)(2)] and [Ag2Br2(mu-S-pySH)(2)(PPh3)(2)] complexes

Lobana TS; Sharma R; Butcher RJ

首页> 外文期刊>Polyhedron: The International Journal for Inorganic and Organometallic Chemistry >Pyridine-2-thione (pySH) derivatives of silver(I): Synthesis and crystal structures of dinuclear [Ag2Cl2(mu-S-pySH)(2)(PPh3)(2)] and [Ag2Br2(mu-S-pySH)(2)(PPh3)(2)] complexes

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Pyridine-2-thione (pySH) derivatives of silver(I): Synthesis and crystal structures of dinuclear [Ag2Cl2(mu-S-pySH)(2)(PPh3)(2)] and [Ag2Br2(mu-S-pySH)(2)(PPh3)(2)] complexes

机译：银（I）的吡啶-2-硫酮（pySH）衍生物：双核[Ag2Cl2（mu-S-pySH）（2）（PPh3）（2）]和[Ag2Br2（mu-S-pySH）的合成和晶体结构（2）（PPh3）（2）]配合物

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Reaction of silver(I) halides with PPh3 in acetonitrile and then with pyridine-2-thione (pySH) chloroform (1:1:1 molar ratio) has yielded sulfur bridged dimers; of general formula, [Ag2X2(mu-S-pySH)(2)(PPh3)(2)] (X = Cl, 1, Br, 2). Both these complexes have been characterized using analytical data, NMR spectroscopy and single crystal X-crystallography. The central Ag2S2 cores form parallelograms with unequal Ag-S bond distances (2.5832(8), 2.7208(11) angstrom) in 1 and (2.6306(4), 2.6950(7) angstrom) in 2, respectively. The Ag center dot center dot center dot Ag contacts of compounds 1 and 2 are 3.8425(8) and 3.821](4) angstrom, respectively. The angles around Ag (in the range 87.19(2)-121.71(2)degrees in 1 and 87.81(2)-121.53(2)degrees in 2) reveal highly distorted tetrahedral geometry. There are inter dimer pi-pi stacking interactions between pyridyl rings (inter ring distances of 3.498 and 3.510 angstrom in complexes 1 and 2, respectively). The solution state P-31 NMR spectroscopy has shown the existence of both monomers and dimers. The studies reveal relatively weaker intramolecular -NH center dot center dot center dot Cl hydrogen bonding in case of AgCl vis-a-vis that in CuCl which favored both a monomer and a dimer with AgCl, and only a monomer with CuCl. (C) 2008 Elsevier Ltd. All rights reserved.

机译：卤化银（I）与PPh3在乙腈中，然后与吡啶-2-硫酮（pySH）氯仿（摩尔比为1：1：1）反应，生成硫桥连二聚体;通式[Ag2X2（mu-S-pySH）（2）（PPh3）（2）]（X = Cl，1，Br，2）。这两种配合物均已使用分析数据，NMR光谱和单晶X晶体学进行了表征。中心的Ag2S2芯形成平行四边形，其不等的Ag-S键距分别为（2.5832（8），2.7208（11）埃）和（2.6306（4），2.6950（7）埃）。化合物1和2的Ag中心点中心点中心点Ag接触点分别为3.8425（8）和3.821]（4）埃。 Ag周围的角度（在1中为87.19（2）-121.71（2）度和在2中为87.81（2）-121.53（2）度）揭示了高度扭曲的四面体几何形状。吡啶基环之间存在二聚体间pi-pi堆积相互作用（复合物1和2中的环间距离分别为3.498和3.510埃）。溶液状态的P-31 NMR光谱表明存在单体和二聚体。研究表明，在AgCl的情况下，分子内-NH中心点中心点中心氢键Cl的氢键相对较弱，而在CuCl中，AgCl既有利于单体和二聚体，也仅有利于CuCl单体。（C）2008 Elsevier Ltd.保留所有权利。

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《Polyhedron: The International Journal for Inorganic and Organometallic Chemistry》 |2008年第5期|共6页
作者
Lobana TS; Sharma R; Butcher RJ;
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正文语种 eng
中图分类化学;
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silver(I); pyridine-2-thione; triphenyl phosphine; crystal structure; HETEROCYCLIC THIONES; TERTIARY PHOSPHINES; MONONUCLEAR COMPLEXES; BRIDGING LIGANDS; NITRATE; COUNTERIONS; THIOAMIDES; COPPER(I); POLYMERS; NETWORK;

机译：银（I）;吡啶-2-硫酮;三苯基膦;晶体结构;杂环亚硫醚;叔膦;单核络合物;架桥基;硝酸盐;抗衡离子;硫酰胺;铜（I）;聚合物;网络;

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Pyridine-2-thione (pySH) derivatives of silver(I): Synthesis and crystal structures of dinuclear [Ag2Cl2(mu-S-pySH)(2)(PPh3)(2)] and [Ag2Br2(mu-S-pySH)(2)(PPh3)(2)] complexes

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