Metal-heterocyclic thione interactions.: 13.: Pyridine-2-thione derivatives of copper(I):: crystal structure of dinuclear [bromo(pyridine-2-thione)(tri-p-tolylphosphine)copper(I)]2 complex
Metal-heterocyclic thione interactions.: 13.: Pyridine-2-thione derivatives of copper(I):: crystal structure of dinuclear [bromo(pyridine-2-thione)(tri-p-tolylphosphine)copper(I)]2 complex
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DOI：
10.1016/s0277-5387(02)01006-9
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发表时间：
2002-07-01
期刊：
影响因子：
2.6
通讯作者：
Castineiras, A
中科院分区：
文献类型：
--
作者：
Lobana, TS;Castineiras, A
以不溶CuBr2(C5H5NS)(2){由溴化铜（II）和吡啶-2-硫酮（C5H5NS）在乙醇中与过量的三对甲基膦（P -tol (3)P）在氯仿中（1:2摩尔比）反应制备了硫桥双核铜(1)配合物[CuBr(eta(2)-S-mu-C5H5NS)(P -tol (3)P)](2)(1)。同样地，制备了其他化学计量铜(l)配合物[CuX(C5H5NS)(Ph3P)](2) {X = Cl， 2和1,3。化合物I由二氯甲烷-氯仿-甲醇混合物结晶而成，以中心对称的硫桥二聚体的形式存在，每个Cu原子具有扭曲的四面体几何形状，每个Cu原子的其他两个位置由P - tol (3)P中的P原子和溴原子占据。该二聚体的核心Cu2S2为平行四边形，重要原子间参数为：Cu-P， 2.2376(13), Cu-S, 2.3895(19), 2.415(2), Cu-Br, 2.4455(1), S-C(2), 1.717(4), Cu-Cu*, 3.250(2), S-S*, 3.539(3)埃；Cu-S-Cu * 85.14 (6) S-Cu-S * 94.86 (6), Cu-S-C(2)。108.41(14), 113.12(16)度。二聚体结构通过强的分子内N-H…Br氢键[3.319(5)埃]。x射线研究表明，2在晶体生长过程中转变为单体[CuCl(eta(1)-S-mu-C5H5NS)(Ph3P)(2)](4)。强分子内N-H…Cl氢键似乎稳定了单体。所有化合物都使用分析数据，红外和远红外（4000-100 cm(-1)），紫外-可见光谱，核磁共振（H-1, C-13）和x射线晶体学进行了表征。控制铜的因素…描述了铜在硫桥双核铜-杂环硫酮配合物中的相互作用。(C) 2002 Elsevier Science Ltd.版权所有。
The sulfur-bridged dinuclear copper (1) complex, [CuBr(eta(2)-S-mu-C5H5NS)(p-Tol(3)P)](2) (1) was prepared by the reaction of insoluble CuBr2(C5H5NS)(2) {from copper(II) bromide and pyridine-2-thione(C5H5NS) in ethanol} with excess tri-p-tolylphosphine (p-Tol(3)P) in chloroform (1:2 mole ratio). Similarly, other copper(l) complexes of stoichiometry [CuX(C5H5NS)(Ph3P)](2) {X = Cl, 2 and 1, 3 were prepared. Compound I crystallised from a dichloromethane-chloroform-methanol mixture and exists as a centrosymmetric sulfur-bridged dimer with distorted tetrahedral geometry about each Cu atom the other two positions of each Cu atom being occupied by a P atom from p-Tol(3)P and a bromine atom. The central core Cu2S2 of the dimer is a parallelogram with the important interatomic parameters as follows: Cu-P, 2.2376(13), Cu-S, 2.3895(19), 2.415(2), Cu-Br, 2.4455(l 1), S-C(2), 1.717(4), Cu-Cu*, 3.250(2), S-S*, 3.539(3) Angstrom; Cu-S-Cu*, 85.14(6), S-Cu-S*, 94.86(6), Cu-S-C(2). 108.41(14), 113.12(16)degrees. The dimer structure is stabilised by strong intramolecular N-H...Br hydrogen bonds [3.319(5) Angstrom]. The X-ray Study of 2 showed that it has transformed into monomer [CuCl(eta(1)-S-mu-C5H5NS)(Ph3P)(2)] (4) during crystal growth. The strong intramolecular N-H...Cl hydrogen bonding appears to stabilise the monomer. All the Compounds were characterised using analytical data, IR and far-IR (4000-100 cm(-1)), UV-Vis spectra, NMR (H-1, C-13) and for I and 4 using X-ray crystallography. The factors controlling Cu...Cu interaction in the sulfur-bridged dinuclear copper(l)-heterocyclic thione complexes are described. (C) 2002 Elsevier Science Ltd. All rights reserved.