Fine Electronic State Tuning of Cobaltadithiolene Complexes by Substituent Groups on the Benzene Ring
Fine Electronic State Tuning of Cobaltadithiolene Complexes by Substituent Groups on the Benzene Ring
复制标题
通过苯环上的取代基对二硫杂环戊二烯钴配合物进行精细电子态调控
作者：
sukada;S.; Kondo;M.; Sato;H.; Gunji;T
一系列 3,6- 和 4,5-二卤素取代的 1,2-苯二硫醇 (H2bdt) 配体，(3,6-X12-4,5-X22-1,2-H2bdt) (X2= H, X1=F (1a), Cl (1b), Br (1c); X1= H, X2= Cl (4)) 及其钴配合物 [Cp*Co(3,6-X12-4,5-X22-1,2-bdt)] (X2= H, X1=F (2a), Cl (2b), Br (2c); X1= H, X2= Cl (5)) 通过改进的选择性硫醇化反应合成。还合成了 1,2-二苯基取代的二硫杂环钴配合物 (2d)。所有钴二硫烯配合物的分子结构均通过单晶X射线衍射分析确定。化合物2a、5和12显示出具有分子间相互作用的独特堆积结构，这证实它们是具有Cp*配体的半夹心型金属二硫烯配合物的第一个例子。使用紫外可见光谱测量和循环伏安法研究了苯取代基类型和位置对金属二硫烯环的影响。结果表明，苯环3、6位卤素原子取代对二硫醇环的影响大于4、5位卤素原子取代。
A series of 3,6- and 4,5-dihalogen-substituted 1,2-benzenedithiol (H2bdt) ligands, (3,6-X12-4,5-X22-1,2-H2bdt) (X2= H, X1= F (1a), Cl (1b), Br (1c); X1= H, X2= Cl (4)), and their cobalt complexes, [Cp∗Co(3,6-X12-4,5-X22-1,2-bdt)] (X2= H, X1= F (2a), Cl (2b), Br (2c); X1= H, X2= Cl (5)), were synthesized by a modified selective thiolation reaction. The 1,2-diphenyl-substituted cobaltadithiolene complex (2d) was also synthesized. The molecular structures of all cobaltadithiolene complexes were determined by single crystal X-ray diffraction analysis. Compounds2a,5and12showed unique packing structures with intermolecular interactions that confirmed them as the first examples of half-sandwich-type metalladithiolene complexes with a Cp∗ligand. The effects of the benzene substituent type and position on the metalladithiolene ring were investigated using UV–vis spectroscopy measurements and cyclic voltammetry. The results indicate that substitution of halogen atoms at the 3 and 6 position of the benzene ring had a larger effect on the dithiolene ring than substitution at the 4 and 5 positions.