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Ab initio Study on Structures and Isomerization of Magnesium Fluorosilylenoid H2SiFMgF
Yi-jian Zhang,Mei-jiang Li,Guo-qiao Lai,Da-cheng Feng,Sheng-yu Feng*
Author NameAffiliationE-mail
Yi-jian Zhang Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education,Hangzhou Normal University, Hangzhou 310012, China  
Mei-jiang Li Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education,Hangzhou Normal University, Hangzhou 310012, China  
Guo-qiao Lai Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education,Hangzhou Normal University, Hangzhou 310012, China  
Da-cheng Feng School of Chemistry and Chemical Engineering, Shandong University, Ji'nan 250100, China  
Sheng-yu Feng* Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education,Hangzhou Normal University, Hangzhou 310012, ChinaSchool of Chemistry and Chemical Engineering, Shandong University, Ji'nan 250100, China fsy@sdu.edu.cn 
Abstract:
The structures and isomerization of magnesium fluorosilylenoid H2SiFMgF were investigated by ab initio molecular orbital theory. Four equilibrium structures and three isomeric transition states were located and fully optimized at the B3LYP/6-31G(d,p) and G3MP2B3 levels, respectively. Based on the B3LYP/6-31G(d,p) optimized geometries, harmonic frequencies of various structures were obtained and 29Si chemical shifts were calculated. The solvent effects were investigated by means of the polarizable continuum model using THF as a solvent at B3LYP/6-31G(d,p) level. Isomerization paths for isomers were confirmed by intrinsic reaction coordinate calculations. The calculated results show that tetrahedral structure has the lowest energy and is the most stable; tetrahedral, three-membered ring, and p-complex structures are suggested to be the experimentally detectable ones; and σ-complex structure has the highest energy and will not exist.
Key words:  Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education,Hangzhou Normal University, Hangzhou 310012, China
FundProject:
Ab initio Study on Structures and Isomerization of Magnesium Fluorosilylenoid H2SiFMgF
张义建,李美江,来国桥,冯大诚,冯圣玉*
摘要:
采用从头算分子轨道理论对镁氟类硅烯H2SiFMgF的构型及异构化进行了研究. 在B3LYP/6-31G(d,p)和G3MP2B3水平上找出四种构型及三种过渡态,并进行了全优化. 在B3LYP/6-31G(d,p)的优化参数基础上,得到了各构型的振动频率,计算了e29Si的化学位移.在B3LYP/6-31G(d,p)水平上,以四氢呋喃为溶剂,采用可极化连续模型研究了溶剂化效应. 并采用内察反应坐标方法对过渡态进行了验证. 研究结果表明,四面体结构具有最低的能量,最稳定. 四面体、三元环和p-络合物结构为实验可探测结构,σ-络合物结构具有最高能量,也是不能存在的构型
关键词:  镁氟类硅烯,从头算,B3LYP/6-31G(d,p)理论,异构化
DOI:10.1088/1674-0068/21/06/541-546
分类号: