期刊文献+

R_2C=GeH_2和R_2Ge=CH_2结构与成键特征的理论研究 被引量:2

Theoretical Study on the Structure and Bonding Character of the R_2Ge=CH_2 and R_2C=GeH_2
下载PDF
导出
摘要 用密度泛函理论(DFT),在B3LYP/6-31+G(d,p)水平上研究了取代基对二取代锗烯R2Ge=CH2和R2C=GeH2[R=H,OH,NH2,SH,PH2,F,Cl,Br,(NHCH)2,CH3,(CH)2]的影响.研究发现π供电子取代基在碳上时更能引起分子结构在锗端的锥型化.碳原子上的π电子给予取代基的给电子效应越强,R2C的单-三态能量差越大,π电子的反极化效应就越强,使得化合物的结构在锗端发生的弯曲越明显,从而使得弯曲结构更稳定.和前人的计算相比,碳上的给电子取代基对GeH2结构影响大于它对SiH2的影响. Substituent effects on the disubstituted heavier analogues of R2C=GeH2 and R2Ge=CH2 [R=H, OH, NH2, SH, PH2, F, Cl, Br, (NHCH)2, CH3, (CH)2] were investigated using density functional theory [B3LYP/6-31 +G(d, p)]. The major conclusion was that the stronger the π-donation of the substituents, the larger the AEsT of CR2 and the stronger the π-electron reversed-polarization effect. As the π-electron reversed-polarization effect increased, the distortion of GeH2 fragment increased, and the stability of the bent structure increased. In addition, the π-electron-donating substitution at the carbon atom was more effective at inducing a bent structure than at the Ge atom. In contrast to the R2C = Sill2 system, the π-electron-donating substituents at the carbon atom have more effective influence on inducing GeH2 a bent structure than that of Sill2.
出处 《化学学报》 SCIE CAS CSCD 北大核心 2006年第19期1974-1980,共7页 Acta Chimica Sinica
基金 甘肃省自然科学基金(No.3ZS051-A25-021)资助项目.
关键词 密度泛函理论 锗烯 反极化效应 density functional theory (DFT) germene reversed polarization effect
  • 相关文献

参考文献21

  • 1Davidson,P.J.; Lappert,M.F.J.Chem.Soc.,Chem.Commun.1973,317.
  • 2Brook,A.G.; Abdesaken,F.; Gutekunst,B.; Gutekunst,G.;Kallury,R.K.J.Chem.Soc.,Chem.Commun.1981,191.
  • 3Escudié,J.; Couret,C.; Ranaivonjatovo,H.Coord.Chem.Rev.1998,178,565.
  • 4Chaubon,M.A.; Ranaivonjatovo,H.; Escudié,J.; Satgé,J.Main Group Met.Chem.1996,19,145.
  • 5Tsumuraya,T.; Batcheler,S.A.; Masamune,S.Angew.Chem.,Int.Ed.Engl.1991,32,902.
  • 6Power,P.P.Chem.Rev.1999,99,3463.
  • 7Baines,K.M.; Stibbs,W.G.Coord.Chem.Rev.1995,145,157.
  • 8Baines,K.M.; Stibbs,W.G.Adv.Organomet.Chem.1996,39,275.
  • 9Couret,C.; Escudié,J.; Satgé,J.; Lazraq,M.J.Am.Chem.Soc.1987,109,4411.
  • 10Lazraq,M.; Couret,C.; Escudié,J.; Satgé,J.; Soufiaoui,M.Polyhedron 1991,10,1153.

同被引文献55

引证文献2

二级引证文献5

相关作者

内容加载中请稍等...

相关机构

内容加载中请稍等...

相关主题

内容加载中请稍等...

浏览历史

内容加载中请稍等...
;
使用帮助 返回顶部