DFT investigation of the catalytic hydromethylation of α-olefins by metallocenes.: 1.: Differences between scandium and lutetium in propene hydromethylation

被引：26

作者：

Barros, Noemi

Eisenstein, Odile ^{[1
]}

Maron, Laurent

Tilley, T. Don

机构：

[1] Univ Montpellier 2, Lab Struct & Dynam Syst Mol & Solides, UMR 5636, CNRS,Inst Gerhardt, F-34095 Montpellier 05, France

[2] Univ Toulouse 3, Phys Quant Lab, UMR 5626, CNRS,IRSAMC, F-31062 Toulouse, France

[3] Univ Calif Berkeley, Dept Chem, Berkeley, CA 94720 USA

[4] CEA Valrho, DEN, DRCP, SCPS,LCAM, F-30207 Bagnols Sur Ceze, France

来源：

ORGANOMETALLICS | 2006年 / 25卷 / 24期

关键词：

D O I：

10.1021/om060498z

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

A DFT study of the catalytic properties of Cp2ScCH3 and Cp2LuCH3 in the hydromethylation of propene has been performed. The catalytic behavior of Cp2ScCH3 is confirmed, and the formation of secondary products is rationalized. It is shown that Cp2LuCH3 cannot exhibit catalytic behavior and that only stoichiometric conversion of propene to isobutane could be observed. The difference in reactivities between the two metallocenes has been investigated, and an electronic explanation is given based on differences in the coordination of propene. However, the intrinsic reactivities of the two metallocenes is proposed to be driven by both electronic and steric effects.

引用

页码：5699 / 5708

页数：10

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