ⅡB族金属dmit,dmid配合物的傅里叶拉曼光谱研究  

Studies on FT-Raman Spectra of ⅡB-Metal Complexes with Ligand Dmit and Dmid

作　　者：卞国庆[1] 朱琴玉[1] 李晓伟[1] 戴洁[1] 顾仁敖[1] 

机构地区：[1]苏州大学化学系,江苏苏州215006

出　　处：《光谱学与光谱分析》2005年第3期409-411,共3页Spectroscopy and Spectral Analysis

基　　金：国家自然科学基金 (2 0 0 71 0 2 4 ;2 0 371 0 33)资助项目

摘　　要：通过改变配体结构、改变金属离子等方法研究了ⅡB族金属不对称二硫纶配合物 [Me4N]2 [MLn(SPh) 2 ](M =Zn ,Cd ;L1=dmit=1,3 二硫盐 4 ,5 二硫醇盐 2 硫酮盐 ,L2 =dmid =1,3 二硫盐 4 ,5 二硫醇盐 2 酮盐 )和 [Bu4N]2 [Zn(dmit) 2 ]的固体粉末傅里叶拉曼 (FT Raman)光谱 ,并对它们进行了逐一比较标识。当配合物中dmit2 -被dmid2 -取代时会使 14 2 0cm-1处CC峰蓝移 38cm-1左右 ;在 990cm-1处的吸收为五元杂环吸收峰 ,当Zn2 + 被Cd2 + 取代、dmit2 -被dmid2 -取代后 ,分别红移 11和 7cm-1。在 4 6 3cm-1左右以及在 30 0cm-1左右的谱峰分别为配体dmit2 -或dmid2 -中 S2 CCS2 骨架上的S—C—S的伸缩振动和变形振动 ,同样随着dmit2 -被PhS-取代、Zn2 + 被Cd2 + 取代而分别红移 ,但是dmid2 -取代dmit2 -时却使此峰蓝移。配合物中的Cd—S有两处振动峰 ,一处为硫酚的硫与Cd键的峰 ,另一处为dmit2 -或dmid2 -上的硫与Cd键的峰 ,分别为 180和 14 0cm-1左右。Zn—S振动峰同样有两种 ,硫酚的硫与Zn键的峰和dmit2 -或dmid2 -上的硫与Zn键的峰 ,它们分别在 193和 15 5cm-1左右。The powder solid state FT-Raman spectra of four unsymmetric dithiolate complexes with formulas (Me_4N)_2[M(L_n)(SPh)_2] (M=Cd and Zn, L_1=dmit=1,3-dithiole-2-thione-4,5-dithiolate, L_2=dmid=1,3-dithiole-2-one-4,5-dithiolate, SPh= thiophenolate) (2-5) and [Bu_4N]_2[Zn(dmit)_2] (1) were studied and characterized by changing the structures of ligands or the metals of the complexes. The blue shift of the CC peak around 1 420 cm -1 is about 38 cm -1 when the dmit 2- is replaced by dmid 2-. When Zn 2+ is replaced by Cd 2+, or dmit 2- is replaced by dmid 2-, the 990 cm -1 peaks of the pentacyclic ring shift to red by about 11 and 7 cm -1 respectively. Two peaks at 463 and 300 cm -1 were assigned to stretching vibration and bending vibration respectively for the S—C—S bond of S_2C CS_2 in dmit 2-or dmid 2-. Red shifts of those two peaks are found when dmit 2- is replaced by SPh-, or Zn 2+ is replaced by Cd 2+; but they will shift to blue when dmit 2- is replaced by dmid 2-. There are two peaks of Cd—S vibrations with the sulfur atom from thiophenolate and from the ligands dmit 2- or dmid 2-, which are at about 180 and 140 cm -1 respectively. Just like Cd—S, the vibration of Zn—S has two peaks as well, which are at about 193 and 155 cm -1, respectively.

关 键 词：配合物 取代 蓝移 拉曼光谱 伸缩振动 红移 CD^2+ 左右 改变 配体 

分 类 号：O657.37[理学—分析化学] O614[理学—化学]