类锗烯H_2GeFAlF_2的结构及其与RH(R=F,OH,NH_2)的插入反应  

Structures of Germylenoid H_2GeFAlF_2 and Its Insertion Reactions with RH(R = F,OH,NH_2)

作　　者：张明霞[1] 焉炳飞 李文佐[1] ZHANG Ming-xia YAN Bing-fei LI Wen-zuo(School of Chemistry and Chemical Engineering, Yantai University, Yantai 264005, Chin)

机构地区：[1]烟台大学化学化工学院,山东烟台264005

出　　处：《烟台大学学报（自然科学与工程版）》2016年第4期258-264,共7页Journal of Yantai University(Natural Science and Engineering Edition)

基　　金：烟台大学青年学术骨干专项基金资助项目;烟台大学研究生科技创新基金重点资助项目(YDZD1607)

摘　　要：采用M06-2X和QCISD方法研究了类锗烯H2Ge FAl F2的结构及其与RH(R=F,OH,NH2)的插入反应.在M06-2X/6-311+G(d,p)水平上对势能面上各个驻点进行了构型优化,并在QCISD/6-311++G(d,p)水平上进行了单点能量计算.结果表明,H2Ge FAl F2存在3种平衡构型,分别是经典四面体构型、p-complex构型和三元环构型,其中p-complex构型能量最低最稳定.对p-complex构型与RH(R=F,OH,NH2)的插入反应进行了理论研究.结果表明,3个插入反应的机理类似,沿着反应势能面,反应物经过一个过渡态和一个中间体到达产物.无论从热力学还是动力学角度,H2Ge FAl F2与HF的反应都最容易进行.研究了溶剂化效应对插入反应的影响,结果表明,THF溶剂抑制了反应的进行.The structures of the germylenoid H2GeFAlF2and its insertion reactions with RH （R = F, OH, NH2） are studied using the M06-2X and QCISD methods. The stationary points along the potential energy surfaces are optimized at the level of M06-2X/6-311 ＋ G （d, p）, and the single point energies are calculated at QCISD/6-311 ＋ ＋ G （d, p） level of theory. The results demonstrated that for H2GeFA1F2, there were three equilibrium structures, the classical tetrahedral structure, the p-complex structure and the three-membered ring structure, in which the pcomplex structure is the most stable with lowest energy. The insertion reactions of the p-complex structure with RH （ R = F, OH, NH2 ） are investigated theoretically. The results indicate that the three insertion reactions are similar. Along the potential energy surface, the reactants reach the products through one transition state and one intermediate. The insertion reaction of H2GeFAlF2with HF is the easiest both thermodynamically and dynamically. The solvent effects upon the insertion reactions are considered, and the results indicate that the insertion reactions are unfavorable in THF solvent.

关 键 词：类锗烯H2GeFAlF2 平衡构型 RH(R=F OH NH2) 插入反应 

分 类 号：O641.12[理学—物理化学]