Crystal structure and solution studies of the product of the reaction of β-mercaptoethanol with vanadate
Crystal structure and solution studies of the product of the reaction of β-mercaptoethanol with vanadate
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DOI：
10.1139/cjc-77-12-2088
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发表时间：
1999-12-01
期刊：
影响因子：
--
通讯作者：
Tracey, AS
中科院分区：
文献类型：
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作者：
Bhattacharyya, S;Batchelor, RJ;Tracey, AS
β-巯基乙醇与钒酸盐在弱碱性条件下反应，得到结晶复合物，并通过 X 射线衍射和 FTIR 光谱进行了表征。该配合物在结构上是二聚体，具有中心[VO](2)核心和围绕每个钒原子的五配位、粗略的三角双锥体排列，并且硫占据假轴位置。当该复合物溶解在水、氯仿或乙腈中时，观察到单个 V-51 NMR 信号。乙腈对钒化学位移的巨大影响表明与乙腈发生反应的可能性。 FTIR 显示乙腈溶液中存在两种配合物，但氯仿或水中仅存在一种。为了进一步表征溶液复合物，进行了混合溶剂研究。 [{VO2(OC2H4S)}(2)][NEt4](2)晶体结构：单斜晶系，空间群P2(1)/n,。 a = 8.3451(17)，b = 16.954(4)，c = 10。2064(25)埃； β = 101. 271(18) 度； V = 1416.2 埃(3)； Z = 2;对于 1355 个数据（I-o 大于或等于 2.5 sigma (I-o)）和 147 个变量，R-F = 0.048。
Reaction of beta-mercaptoethanol with vanadate under slightly alkaline conditions provided a crystalline complex that was characterized by X-ray diffraction and FTIR spectroscopy. The complex was dimeric in structure with a central [VO](2) core and a pentacoordinate, crudely trigonal bipyramidal arrangement about each vanadium atom with a sulphur occupying a pseudo-axial position. A single V-51 NMR signal was observed for this complex when dissolved in water, chloroform or acetonitrile. A large influence of acetonitrile on the vanadium chemical shift suggested the possibility of reaction with acetonitrile. FTIR showed the presence of two complexes in acetonitrile solution but only one in chloroform or water. Mixed solvent studies were carried out in an effort to further characterize the solution complexes. Crystal structure of [{VO2(OC2H4S)}(2)][NEt4](2): monoclinic, space group P2(1)/n,. a = 8.3451(17), b = 16.954(4), c = 10. 2064(25) Angstrom; beta = 101. 271(18)degrees; V = 1416.2 Angstrom(3); Z = 2; R-F = 0.048 for 1355 data (I-o greater than or equal to 2.5 sigma (I-o)) and 147 variables.