Sources of error in DFT computations of C-C bond formation thermochemistries:: π→σ transformations and error cancellation by DFT methods

被引：162

作者：

Pieniazek, Susan N. ^{[1
]}

Clemente, Fernando R. ^{[1
]}

Houk, Kendall N. ^{[1
]}

机构：

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

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2008年 / 47卷 / 40期

基金：

美国国家科学基金会;

关键词：

addition reactions; computational chemistry; density functional calculations; hydrocarbons; thermochemistry;

D O I：

10.1002/anie.200801843

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Alarming: Multiple sources of errors in DFT energetics of C-C bond-forming reactions were investigated by evaluating structural transformations in Diels-Alder reactions: conversion of π into σ bonds and changes in conjugation, hyperconjugation, and branching interactions. A startling overestimation of the π to σ bond conversion is found with most methods, a central problem to all reactions involving addition of π bonds (electrocyclic processes, ene, aldol). © 2008 Wiley-VCH Verlag GmbH & Co. KGaA.

引用

页码：7746 / 7749

页数：4

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