西北师范大学学报（自然科学版）2011，Vol.47Issue(1)：63-69,7.
Pt-(-)-sparteine配合物催化二级醇的氧化动力学拆分的理论研究
The theoretical investigation of oxidative kinetic resolution of secondary alcohols catalyzed by Pt-(-)-sparteine complexes
摘要
Abstract
Using the B3LYP method of density function theory with 6-31G(d,p) and LAN L2DZ basis sets,the mechanism of oxidative kinetic resolution of secondary alcohols (1-phenylethanol) catalyzed by (-)-sparteine-PtCl2 complexes has been characterized in detail. The results indicate that the reaction processes comprise the coupling 1-phenylethanol with catalysts, deprotonation and β-hydride elimination whether it is (R)-phenylethanol or (S)-phenylethanol. Meanwhile, the β-hydride elimination acts as the determining step in the reaction. As compared the structures and energies of (R)-phenylethanol with (S)-phenylethanol catalyzed by (-)-sparteine-PtCl2 complexes in gaseous phase, the strong interactions ofβ-agostic and hyper conjugation effect of Pt-O→ C-Hβ in the determining step generate more stable state of TS2R, also the selectivity is calculated of 15. 18. Moreover, the effects of toluene and chloroform solvents are investigated by PCM method. The calculations show an increase in dielectric strength,however, the decrease of the energies for rate determining step as well as the selectivity. (-)-Sparteine-PtCl2 is not a good catalyst when compared with the (-)-sparteine-PdCl2 complexes in oxidative kinetic resolution of secondary alcohols.关键词
二级醇/氧化动力学拆分/选择性/铂类配合物/密度泛函分类
化学化工引用本文复制引用
耿志远,吴建花,王永成,王秀红,周婧,刘宏强..Pt-(-)-sparteine配合物催化二级醇的氧化动力学拆分的理论研究[J].西北师范大学学报（自然科学版）,2011,47(1):63-69,7.基金项目
甘肃省自然科学基金资助项目(0710RJZ114) （0710RJZ114）
甘肃省教育厅研究生导师科研基金资助项目(0801-10) （0801-10）
