Spin-coupled study of the electronic mechanism of the hetero-diels-alder reaction of acrolein and ethene

J J  Blavins; D L  Cooper; P B  Karadakov

doi:10.1021/jp047431e

Spin-coupled study of the electronic mechanism of the hetero-diels-alder reaction of acrolein and ethene

J J Blavins, D L Cooper, P B Karadakov

Chemistry

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

Abstract

Modern valence bond theory, in its spin coupled form. is used to elucidate the electronic rearrangements that take place during the Course of the gas-phase hetero-Diels-Alder cycloaddition reaction of s-cis-acrolein (cis-1-oxabutuadiene or cis-propeneal) and ethene. It is found that the most dramatic changes to the electronic structure occur in a relatively narrow interval of the reaction pathway soon after the transition state and that the system passes through a geometry at which it can be considered to be significantly aromatic. Although concerted. the reaction is markedly asynchronous. with the breaking of the carbon-oxygen pi bond and the formation of the new carbon-oxygen sigma bond. "lagging behind" somewhat the other bond-making and bond-breaking processes.

Original language	English
Pages (from-to)	231-235
Number of pages	5
Journal	Journal of Physical Chemistry A
Volume	109
Issue number	1
DOIs	https://doi.org/10.1021/jp047431e
Publication status	Published - 13 Jan 2005

Keywords

BOND ORDER
VALENCE

Access to Document

10.1021/jp047431e

Cite this

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title = "Spin-coupled study of the electronic mechanism of the hetero-diels-alder reaction of acrolein and ethene",

abstract = "Modern valence bond theory, in its spin coupled form. is used to elucidate the electronic rearrangements that take place during the Course of the gas-phase hetero-Diels-Alder cycloaddition reaction of s-cis-acrolein (cis-1-oxabutuadiene or cis-propeneal) and ethene. It is found that the most dramatic changes to the electronic structure occur in a relatively narrow interval of the reaction pathway soon after the transition state and that the system passes through a geometry at which it can be considered to be significantly aromatic. Although concerted. the reaction is markedly asynchronous. with the breaking of the carbon-oxygen pi bond and the formation of the new carbon-oxygen sigma bond. {"}lagging behind{"} somewhat the other bond-making and bond-breaking processes.",

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T1 - Spin-coupled study of the electronic mechanism of the hetero-diels-alder reaction of acrolein and ethene

AU - Blavins, J J

AU - Cooper, D L

AU - Karadakov, P B

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Y1 - 2005/1/13

N2 - Modern valence bond theory, in its spin coupled form. is used to elucidate the electronic rearrangements that take place during the Course of the gas-phase hetero-Diels-Alder cycloaddition reaction of s-cis-acrolein (cis-1-oxabutuadiene or cis-propeneal) and ethene. It is found that the most dramatic changes to the electronic structure occur in a relatively narrow interval of the reaction pathway soon after the transition state and that the system passes through a geometry at which it can be considered to be significantly aromatic. Although concerted. the reaction is markedly asynchronous. with the breaking of the carbon-oxygen pi bond and the formation of the new carbon-oxygen sigma bond. "lagging behind" somewhat the other bond-making and bond-breaking processes.

AB - Modern valence bond theory, in its spin coupled form. is used to elucidate the electronic rearrangements that take place during the Course of the gas-phase hetero-Diels-Alder cycloaddition reaction of s-cis-acrolein (cis-1-oxabutuadiene or cis-propeneal) and ethene. It is found that the most dramatic changes to the electronic structure occur in a relatively narrow interval of the reaction pathway soon after the transition state and that the system passes through a geometry at which it can be considered to be significantly aromatic. Although concerted. the reaction is markedly asynchronous. with the breaking of the carbon-oxygen pi bond and the formation of the new carbon-oxygen sigma bond. "lagging behind" somewhat the other bond-making and bond-breaking processes.

KW - BOND ORDER

KW - VALENCE

U2 - 10.1021/jp047431e

DO - 10.1021/jp047431e

M3 - Article

SN - 1089-5639

VL - 109

SP - 231

EP - 235

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

IS - 1

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