Regarding the stability of d0 monocyclopentadienyl zirconium acetamidinate complexes bearing alkyl substituents with β-hydrogens

被引：52

作者：

Keaton, RJ ^{[1
]}

Koterwas, LA ^{[1
]}

Fettinger, JC ^{[1
]}

Sita, LR ^{[1
]}

机构：

[1] Univ Maryland, Dept Chem & Biochem, College Pk, MD 20742 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2002年 / 124卷 / 21期

关键词：

D O I：

10.1021/ja017294o

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The monocyclopentadienyl zirconium acetamidinate complexes, (η5-C5Me5)Zr[N(R-1)C(Me)N(R-2)]R-3R-4 (1-8), have been shown to be remarkably resistant to β-hydrogen eliminations/abstractions, including the tert-butyl derivative, 3 (R1 = R2 = Cy, R3 = t-Bu, R4 = Cl), which resists both decomposition and isomerization in solution to temperatures of at least 100 °C. Further, two striking examples of an apparent preference for alternative hydrogen-atom abstractions in which complexes 1 and 7/8 that bear isomeric dibutyl substituents are transformed at elevated temperatures to complexes 9 and 10/11 that contain the isomeric butadiene and trimethylenemethane (TMM) C4 fragments, respectively, are presented. These results serve to not only introduce a new ligand environment for zirconium in which β-hydrogen elimination/abstraction processes are substantially retarded, but they further document the availability of alternative low-energy hydrogen abstraction pathways for group 4 alkyl complexes. Copyright © 2002 American Chemical Society.

引用

页码：5932 / 5933

页数：2

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