摘要
采用量子化学从头算理论在MP2/6-31G(d,p)水平上对2,2'-二甲基-4,4'-联噻唑顺反异构体,trans-2,2'-二甲基-4,4'-联噻唑-CHCl3(I),cis-2,2'-二甲基-4,4'-联噻唑-CHCl3(II)形成的1∶1氢键复合物进行计算研究.结果表明,2,2'-二甲基-4,4'-联噻唑在气相条件下,反式构象比顺式构象稳定.氯仿与2,2'-二甲基-4,4'-联噻唑形成的复合物存在较强的氢键,表现为氮原子的孤对电子与氯仿分子中C—H反键σ轨道的相互作用,另外形成C—H…Cl弱相互作用,氢键作用使2,2'-二甲基-4,4'-联噻唑的顺式结构在氯仿溶剂比反式结构更稳定.
The cis-trans isomers of 2,2＇-dimethyl-4,4＇-bithiazole, 1 ： 1 hydrogen-bond complex （I） between trans-2,2＇-dimethyl-4,4＇-bithiazole and chloroform, and hydrogen-bond complex （II） between cis-2,2＇- dimethyl-4,4＇-bithiazole and chloroform were studied by using ab initio calculation at MP2/6-31G（d,p） basis set level. The results showed that in the gas phase, trans-2,2＇-dimethyl-4,4＇-bithiazole was more stable than cis-2,2＇-dimethyl-4,4＇-bithiazole. There are strong hydrogen-bonds existing in the 1 ：1 hydrogen-bond complexes, as interaction between the lone pair electrons on the N atom and σ^＊（C--H） antibonding orbitals in chloroform molecule, as well as weak interaction between C--H and CI. The existing hydrogen-bonds made cis-2,2＇-dimethyl-4,4＇-bithiazole more stable in chloroform solvent.
出处
《化学学报》
SCIE
CAS
CSCD
北大核心
2009年第9期923-928,共6页
Acta Chimica Sinica
基金
吉林省科技发展计划(No.20040569)
教育部高校博士学科点专项科研基金(No.20050184002)资助项目
