富勒烯衍生物C_(50)X(X=SiH_2,PH,S)的结构及稳定性的理论研究  

Theoretical Study of Structure and Stability of Fullerene Derivatives C_(50)X(X=SiH_2,PH,S)

作　　者：许秀芳[1] 尚贞锋[1] 李瑞芳[1] 赵学庄[1] 

机构地区：[1]南开大学化学系,天津300071

出　　处：《高等学校化学学报》2008年第12期2413-2419,共7页Chemical Journal of Chinese Universities

基　　金：国家"九七三"计划(批准号:2006CB932900)资助

摘　　要：用从头算HF/3-21G方法研究了C50的环加成衍生物C50X(X=SiH2,PH,S)所有可能的异构体的结构与稳定性,计算结果表明,SiH2基团、PH基团与S原子在C50上环加成的优先加成位置相同,都为C3—C4类键和C4—C4类键,并且相应形成[5,6]-闭环和[5,5]-闭环结构的最稳定异构体;决定C50X(X=SiH2,PH,S)各异构体稳定性的主要因素,因加成位置以及发生加成反应的C—C键的单双键类型的不同,可能是张力、共轭效应或者二者的共同作用.进一步比较了C50X(X=SiH2,PH,S)与C50X(X=CH2,NH,O)的结构和稳定性等,并总结出规律性的结论,即加成原子的大小和加成位置C—C键的类型是影响形成开环或闭环结构的C50环加成衍生物的两种主要因素.The structure and stability of all possible isomers of C50X（X=SiH2,PH,S）were investigated by ab initio HF/3-21G calculations.The calculation results indicate that the preferred position for cycloaddition of SiH2,PH,and S on C50 is consistent,i.e.on the C3—C4 and C4—C4 sites of C50,and the resultant most stable cycloaddition isomers are [5,6]-closed and [5,5]-closed structures.The main driving force governing the stability of the C50X（X=SiH2,PH,S）isomers is the strain,or the conjugative effect,or the combination of strain and conjugative effect,depending on the addition positions and the types of the attacked C—C bonds.Further,the structures and stabilities of C50X（X=SiH2,PH,S）are compared with those of the C50X（X=CH2,NH,O）,and a general conclusion are drawn：the size of the attacking atom and the type of the attacked C—C bond are two decisive factors for the formation of open or closed structure of the C50X isomer.

关 键 词：C50环加成衍生物 结构 稳定性 

分 类 号：O641[理学—物理化学]