Molecular Modeling of ruthenium alkylidene mediated olefin metathesis reactions. DFT study of reaction pathways

被引：90

作者：

Fomine, S ^{[1
]}

Vargas, SM ^{[1
]}

Tlenkopatchev, MA ^{[1
]}

机构：

[1] Univ Nacl Autonoma Mexico, Inst Invest Mat, CU, Mexico City 04510, DF, Mexico

来源：

ORGANOMETALLICS | 2003年 / 22卷 / 01期

关键词：

D O I：

10.1021/om020581w

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Three possible reaction pathways have been studied for the Cl-2(PMe3)(2)Ru=CH2 and Cl-2(PCY3)(2)Ru=CH2 (Cy = cyclohexyl) mediated metathesis reaction of propylene by quantum-mechanical DFT calculations. It was found that in all cases the metathesis reaction proceeds via dissociative substitution of a phosphine ligand with propylene, giving a monophosphine complex. This tendency increases with ligand volume, and in the case of smaller PMe3 groups it is the entropy contribution to the reaction energetics that causes the monophosphine complex to participate in the metathesis reaction, according to the modeling data.

引用

页码：93 / 99

页数：7

共 52 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]

Adlhart C, 2000, HELV CHIM ACTA, V83, P2192, DOI 10.1002/1522-2675(20000906)83:9<2192::AID-HLCA2192>3.0.CO

[3]

2-G

[4] Mechanistic studies of olefin metathesis by ruthenium carbene complexes using electrospray ionization tandem mass spectrometry [J].

Adlhart, C ;

Hinderling, C ;

Baumann, H ;

Chen, P .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2000, 122 (34) :8204-8214

[5] A new definition of cavities for the computation of solvation free energies by the polarizable continuum model [J].

Barone, V ;

Cossi, M ;

Tomasi, J .

JOURNAL OF CHEMICAL PHYSICS, 1997, 107 (08) :3210-3221

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

BECKE, AD .

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

[7] A theoretical study of homogeneous Ziegler-Natta catalysis [J].

Bernardi, F ;

Bottoni, A ;

Miscione, GP .

ORGANOMETALLICS, 1998, 17 (01) :16-24

[8] Homogeneous metathesis polymerization by well-defined group VI and group VIII transition-metal alkylidenes: Fundamentals and applications in the preparation of advanced materials [J].

Buchmeiser, MR .

CHEMICAL REVIEWS, 2000, 100 (04) :1565-1604

[9] Solvent effect on the optical properties of [(NH3)5Ru-pyrazine]+m (m=2,3) complexes by ab initio calculations [J].

Cacelli, I ;

Ferretti, A .

JOURNAL OF CHEMICAL PHYSICS, 1998, 109 (19) :8583-8590

[10] Mechanism of ruthenium-catalyzed olefin metathesis reactions from a theoretical perspective [J].

Cavallo, L .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (30) :8965-8973

← 1 2 3 4 5 6 →