Why trimerization?: Computational elucidation of the origin of selective trimerization of ethene catalyzed by [TaCl3(CH3)2] and an agostic-assisted hydride transfer mechanism

被引：103

作者：

Yu, ZX ^{[1
]}

Houk, KN ^{[1
]}

机构：

[1] Univ Calif Los Angeles, Dept Chem & Biochem, Los Angeles, CA 90095 USA

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2003年 / 42卷 / 07期

关键词：

ab initio calculations; agostic interactions; alkenes; ethylene trimerization; tantalum;

D O I：

10.1002/anie.200390215

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Because only then a relatively rapid agostic-assisted hydrogen shift can help to form the product. This is the answer to the question in the title and it results from a computational analysis of the catalytic cycle shown and its alternatives for dimerization, tetramerization, and higher oligomerization.

引用

页码：808 / 811

页数：4

共 44 条

[1] New tantalum-based catalyst system for the selective trimerization of ethene to 1-hexene [J].

Andes, C ;

Harkins, SB ;

Murtuza, S ;

Oyler, K ;

Sen, A .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2001, 123 (30) :7423-7424

[2]

ARAKI Y, 1997, Patent No. 5856612

[3] DENSITY-FUNCTIONAL THERMOCHEMISTRY .3. THE ROLE OF EXACT EXCHANGE [J].

BECKE, AD .

JOURNAL OF CHEMICAL PHYSICS, 1993, 98 (07) :5648-5652

[4] THE SELECTIVE TRIMERIZATION OF ETHYLENE TO HEX-1-ENE [J].

BRIGGS, JR .

JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1989, (11) :674-675

[5] High activity ethylene trimerisation catalysts based on diphosphine ligands [J].

Carter, A ;

Cohen, SA ;

Cooley, NA ;

Murphy, A ;

Scutt, J ;

Wass, DF .

CHEMICAL COMMUNICATIONS, 2002, (08) :858-859

[6] ZIEGLER-NATTA CATALYSIS .1. MECHANISM OF POLYMERIZATION OF ALPHA-OLEFINS WITH ZIEGLER-NATTA CATALYSTS [J].

COSSEE, P .

JOURNAL OF CATALYSIS, 1964, 3 (01) :80-88

[7]

Deckers P. J. W., 2001, ANGEW CHEM, V113, P2584

[8]

Deckers PJW, 2001, ANGEW CHEM INT EDIT, V40, P2516, DOI 10.1002/1521-3773(20010702)40:13<2516::AID-ANIE2516>3.0.CO

[9]

2-V

[10]

Dunning Jr T. H., 1976, MODERN THEORETICAL C, V3, P1, DOI DOI 10.1007/978-1-4757-0887-5_1

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