Spin-coupled valence bond study of the reaction between benzene and a methyl cation

G  Raos; L  Astorri; M  Raimondi; D L  Cooper; J  Gerratt; P B  Karadakov

Spin-coupled valence bond study of the reaction between benzene and a methyl cation

G Raos, L Astorri, M Raimondi, D L Cooper, J Gerratt, P B Karadakov

Chemistry

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

Abstract

We present spin-coupled valence bond calculations on the reaction pathway for the insertion of a methyl cation onto the aromatic system of benzene, leading to the Wheland intermediate C6H6CH3+. Simultaneously with the geometrical rehybridization of the two carbons forming the new substrate-electrophile bond (from sp(2) to sp(3)), we observe the crossing of two spin-coupled potential energy curves; at large separations, these correspond to C6H6 + CH3+ and to C6H6+ + CH3. In the neighborhood of the crossing point, the spin-coupled valence bond wave function obtained by mixing these two orbital configurations switches continuously from the former to the latter.

Original language	English
Pages (from-to)	2886-2892
Number of pages	7
Journal	Journal of Physical Chemistry A
Volume	101
Issue number	15
Publication status	Published - 10 Apr 1997

Keywords

WAVE-FUNCTIONS
ABINITIO

Cite this

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title = "Spin-coupled valence bond study of the reaction between benzene and a methyl cation",

abstract = "We present spin-coupled valence bond calculations on the reaction pathway for the insertion of a methyl cation onto the aromatic system of benzene, leading to the Wheland intermediate C6H6CH3+. Simultaneously with the geometrical rehybridization of the two carbons forming the new substrate-electrophile bond (from sp(2) to sp(3)), we observe the crossing of two spin-coupled potential energy curves; at large separations, these correspond to C6H6 + CH3+ and to C6H6+ + CH3. In the neighborhood of the crossing point, the spin-coupled valence bond wave function obtained by mixing these two orbital configurations switches continuously from the former to the latter.",

keywords = "WAVE-FUNCTIONS, ABINITIO",

author = "G Raos and L Astorri and M Raimondi and Cooper, {D L} and J Gerratt and Karadakov, {P B}",

year = "1997",

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language = "English",

volume = "101",

pages = "2886--2892",

journal = "Journal of Physical Chemistry A",

issn = "1089-5639",

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TY - JOUR

T1 - Spin-coupled valence bond study of the reaction between benzene and a methyl cation

AU - Raos, G

AU - Astorri, L

AU - Raimondi, M

AU - Cooper, D L

AU - Gerratt, J

AU - Karadakov, P B

PY - 1997/4/10

Y1 - 1997/4/10

N2 - We present spin-coupled valence bond calculations on the reaction pathway for the insertion of a methyl cation onto the aromatic system of benzene, leading to the Wheland intermediate C6H6CH3+. Simultaneously with the geometrical rehybridization of the two carbons forming the new substrate-electrophile bond (from sp(2) to sp(3)), we observe the crossing of two spin-coupled potential energy curves; at large separations, these correspond to C6H6 + CH3+ and to C6H6+ + CH3. In the neighborhood of the crossing point, the spin-coupled valence bond wave function obtained by mixing these two orbital configurations switches continuously from the former to the latter.

AB - We present spin-coupled valence bond calculations on the reaction pathway for the insertion of a methyl cation onto the aromatic system of benzene, leading to the Wheland intermediate C6H6CH3+. Simultaneously with the geometrical rehybridization of the two carbons forming the new substrate-electrophile bond (from sp(2) to sp(3)), we observe the crossing of two spin-coupled potential energy curves; at large separations, these correspond to C6H6 + CH3+ and to C6H6+ + CH3. In the neighborhood of the crossing point, the spin-coupled valence bond wave function obtained by mixing these two orbital configurations switches continuously from the former to the latter.

KW - WAVE-FUNCTIONS

KW - ABINITIO

M3 - Article

SN - 1089-5639

VL - 101

SP - 2886

EP - 2892

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

IS - 15

ER -