Quantum mechanical investigation on acceleration of electrocyclic reactions through transition metal catalysis

被引：11

作者：

Nisa, Riffat Un ^{[1
]}

Hashmi, Muhammad Ali ^{[2
]}

Sajjad, Saira ^{[1
]}

Mahmood, Tariq ^{[1
]}

Iqbal, Javed ^{[3
]}

Ayub, Khurshid ^{[1
]}

机构：

[1] COMSATS Inst Informat Technol, Dept Chem, Univ Rd,Tobe Camp, Abbottabad 22060, Pakistan

[2] Victoria Univ Wellington, Sch Chem & Phys Sci, Wellington 6012, New Zealand

[3] Univ Agr Faisalabad, Dept Chem, Faisalabad, Pakistan

来源：

JOURNAL OF ORGANOMETALLIC CHEMISTRY | 2016年 / 808卷

关键词：

Electrocyclic reaction; Transition metal catalysis; Non-concerted reaction; Reductive elimination; Density functional theory calculations; HYDROCARBON PERICYCLIC-REACTIONS; AB-INITIO; (2-FURYL)CARBENE COMPLEXES; CYCLOADDITION REACTIONS; ACTIVATION BARRIERS; REACTION ENERGETICS; CARBONYL-COMPOUNDS; CBS-QB3; METHODS; STANDARD SET; DIELS-ALDER;

D O I：

10.1016/j.jorganchem.2016.02.017

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Acceleration of the electrocyclization of 1,3,5-hexatriene to 1,3-cyclohexadiene through early transition metal catalysis is investigated through quantum mechanical methods. The reaction proceeds in a non-pericyclic fashion involving two fundamental steps of catalysis (oxidative addition and reductive elimination), and the calculated acceleration effect is very large, up to 24 kcal mol(-1). Electrocyclization is highly dependent on the nature, formal oxidation state and coordination number of metal. Ligands are also predicted to show tremendous effect on the activation barrier of a reaction. Lowest activation energy is observed for [Nb(CHD)](+3) (5.63 kcal mol(-1)) where Nb is in its highest possible oxidation state i.e. +5. (C) 2016 Elsevier B.V. All rights reserved.

引用

页码：78 / 86

页数：9

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