Spin-Coupled Description of Aromaticity in the Retro Diels-Alder Reaction of Norbornene

J. Grant Hill; David L. Cooper; Peter B. Karadakov

doi:10.1021/jp800969k

Spin-Coupled Description of Aromaticity in the Retro Diels-Alder Reaction of Norbornene

J. Grant Hill, David L. Cooper, Peter B. Karadakov

Chemistry

Research output: Contribution to journal › Article › peer-review

Abstract

The electronic rearrangements along the lowest-energy path for the gas-phase retro Diels-Alder reaction of norbornene are monitored using spin-coupled theory. We find that the most dramatic changes to the electronic structure occur in a relatively narrow interval in which the system passes through a geometry at which it can be considered to be significantly aromatic. We provide an estimate of the vertical resonance energy. Our results are consistent with the anticipated synchronous "aromatic" nature of this reaction, but we find that the key changes occur a little before the actual transition state is reached.

Original language	English
Pages (from-to)	12823-12828
Number of pages	6
Journal	Journal of Physical Chemistry A
Volume	112
Issue number	50
DOIs	https://doi.org/10.1021/jp800969k
Publication status	Published - 18 Dec 2008

Keywords

VALENCE-BOND DESCRIPTION
CHEMICAL-REACTION MECHANISMS
1,3-DIPOLAR ADDITION
TRANSITION STRUCTURES
ELECTRONIC MECHANISM
FULMINIC ACID
AB-INITIO
ETHENE
CYCLOPENTADIENE
REORGANIZATION

Access to Document

10.1021/jp800969k

http://pubs.acs.org/doi/abs/10.1021/jp800969k

Cite this

@article{2f63a2d345d145f59e738b510b1aed47,

title = "Spin-Coupled Description of Aromaticity in the Retro Diels-Alder Reaction of Norbornene",

abstract = "The electronic rearrangements along the lowest-energy path for the gas-phase retro Diels-Alder reaction of norbornene are monitored using spin-coupled theory. We find that the most dramatic changes to the electronic structure occur in a relatively narrow interval in which the system passes through a geometry at which it can be considered to be significantly aromatic. We provide an estimate of the vertical resonance energy. Our results are consistent with the anticipated synchronous {"}aromatic{"} nature of this reaction, but we find that the key changes occur a little before the actual transition state is reached.",

keywords = "VALENCE-BOND DESCRIPTION, CHEMICAL-REACTION MECHANISMS, 1,3-DIPOLAR ADDITION, TRANSITION STRUCTURES, ELECTRONIC MECHANISM, FULMINIC ACID, AB-INITIO, ETHENE, CYCLOPENTADIENE, REORGANIZATION",

author = "Hill, {J. Grant} and Cooper, {David L.} and Karadakov, {Peter B.}",

year = "2008",

month = dec,

day = "18",

doi = "10.1021/jp800969k",

language = "English",

volume = "112",

pages = "12823--12828",

journal = "Journal of Physical Chemistry A",

issn = "1089-5639",

publisher = "American Chemical Society",

number = "50",

}

TY - JOUR

T1 - Spin-Coupled Description of Aromaticity in the Retro Diels-Alder Reaction of Norbornene

AU - Hill, J. Grant

AU - Cooper, David L.

AU - Karadakov, Peter B.

PY - 2008/12/18

Y1 - 2008/12/18

N2 - The electronic rearrangements along the lowest-energy path for the gas-phase retro Diels-Alder reaction of norbornene are monitored using spin-coupled theory. We find that the most dramatic changes to the electronic structure occur in a relatively narrow interval in which the system passes through a geometry at which it can be considered to be significantly aromatic. We provide an estimate of the vertical resonance energy. Our results are consistent with the anticipated synchronous "aromatic" nature of this reaction, but we find that the key changes occur a little before the actual transition state is reached.

AB - The electronic rearrangements along the lowest-energy path for the gas-phase retro Diels-Alder reaction of norbornene are monitored using spin-coupled theory. We find that the most dramatic changes to the electronic structure occur in a relatively narrow interval in which the system passes through a geometry at which it can be considered to be significantly aromatic. We provide an estimate of the vertical resonance energy. Our results are consistent with the anticipated synchronous "aromatic" nature of this reaction, but we find that the key changes occur a little before the actual transition state is reached.

KW - VALENCE-BOND DESCRIPTION

KW - CHEMICAL-REACTION MECHANISMS

KW - 1,3-DIPOLAR ADDITION

KW - TRANSITION STRUCTURES

KW - ELECTRONIC MECHANISM

KW - FULMINIC ACID

KW - AB-INITIO

KW - ETHENE

KW - CYCLOPENTADIENE

KW - REORGANIZATION

UR - http://www.scopus.com/inward/record.url?scp=58149142824&partnerID=8YFLogxK

U2 - 10.1021/jp800969k

DO - 10.1021/jp800969k

M3 - Article

SN - 1089-5639

VL - 112

SP - 12823

EP - 12828

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

IS - 50

ER -

Spin-Coupled Description of Aromaticity in the Retro Diels-Alder Reaction of Norbornene

Abstract

Keywords

Access to Document

Other files and links

Cite this