Simulation of ethylene insertion in an aluminium catalyst

被引：21

作者：

Reinhold, M ^{[1
]}

McGrady, JE

Meier, RJ

机构：

[1] Univ York, Dept Chem, York YO10 5DD, N Yorkshire, England

[2] DSM Res, NL-6160 MD Geleen, Netherlands

来源：

JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS | 1999年 / 03期

关键词：

D O I：

10.1039/a807809b

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Ethylene insertion into [AlMe{MeC(NMe)(2)}](+) has been studied using quantum mechanical simulations. Both planewave Car-Parrinello and localised basis set DFT calculations predict an insertion barrier of approximately 25 kcal mol(-1), in close agreement with estimates derived from experimental data. The calculated barrier for insertion into a methyl bridged dinuclear aluminium species is over 10 kcal mol(-1) higher, suggesting that the monomeric species is the active catalyst.

引用

页码：487 / 488

页数：2

共 15 条

[1] Ruthenium-catalyzed olefin metathesis: A quantum molecular dynamics study [J].

Aagaard, OM ;

Meier, RJ ;

Buda, F .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1998, 120 (29) :7174-7182

[2]

[Anonymous], [No title captured], DOI DOI 10.1016/0021-9991(92)90277-6

[3] Self-consistent molecular Hartree-Fock-Slater calculations - I. The computational procedure [J].

Baerends, E. J. ;

Ellis, D. E. ;

Ros, P. .

CHEMICAL PHYSICS, 1973, 2 (01) :41-51

[4] Self-consistent molecular Hartree-Fock-Slater calculations - II. The effect of exchange scaling in some small molecules [J].

Baerends, E. J. ;

Ros, P. .

CHEMICAL PHYSICS, 1973, 2 (01) :52-59

[5] DENSITY-FUNCTIONAL EXCHANGE-ENERGY APPROXIMATION WITH CORRECT ASYMPTOTIC-BEHAVIOR [J].

BECKE, AD .

PHYSICAL REVIEW A, 1988, 38 (06) :3098-3100

[6] UNIFIED APPROACH FOR MOLECULAR-DYNAMICS AND DENSITY-FUNCTIONAL THEORY [J].

CAR, R ;

PARRINELLO, M .

PHYSICAL REVIEW LETTERS, 1985, 55 (22) :2471-2474

[7] Cationic aluminum alkyl complexes incorporating amidinate ligands. Transition-metal-free ethylene polymerization catalysts [J].

Coles, MP ;

Jordan, RF .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1997, 119 (34) :8125-8126

[8] Ab initio molecular dynamics study of metallocene catalysed ethylene polymerization .3. Bis- versus mono-cyclopentadienyl metallocenes [J].

Iarlori, S ;

Buda, F ;

Meier, RJ ;

VanDoremaele, GHJ .

MOLECULAR PHYSICS, 1996, 87 (04) :801-815

[9] A combined experimental far-infrared and computational density functional approach applied to aluminum-alkyl cocatalysts [J].

Koglin, E ;

Koglin, D ;

Meier, RJ ;

van Heel, S .

CHEMICAL PHYSICS LETTERS, 1998, 290 (1-3) :99-104

[10] A unified view of ethylene polymerization by d0 and d0fn transition metals.: Part 2:: Chain propagation [J].

Margl, P ;

Deng, LQ ;

Ziegler, T .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1998, 120 (22) :5517-5525

← 1 2 →