AGOSTIC ASSISTANCE TO OLEFIN INSERTION IN ALKYLZIRCONOCENE CATIONS - A MOLECULAR-ORBITAL STUDY BY THE EXTENDED HUCKEL-METHOD

被引：115

作者：

PROSENC, MH

JANIAK, C

BRINTZINGER, HH

机构：

[1] UNIV CONSTANCE, FAK CHEM, W-7750 CONSTANCE, GERMANY

[2] BASF AG, KUNSTSTOFF LAB, W-6700 LUDWIGSHAFEN, GERMANY

来源：

ORGANOMETALLICS | 1992年 / 11卷 / 12期

关键词：

D O I：

10.1021/om00060a019

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Alternative reaction modes for alpha-olefin insertion in a zirconocene alkyl cation are investigated by the extended Huckel MO method. Agostic interaction of one of the alpha-H atoms of the migrating alkyl group with the Zr center is found to stabilize the transition state of the preferred reaction mode. Essential contributions to this preference are identified by fragment-MO analysis. Implications of these findings for stereoselective olefin polymerization by chiral ansa-metallocene derivatives are discussed.

引用

页码：4036 / 4041

页数：6

共 52 条

[1] COUNTERINTUITIVE ORBITAL MIXING IN SEMI-EMPIRICAL AND ABINITIO MOLECULAR-ORBITAL CALCULATIONS [J].