Reaction-Surface Topography for Hydride Transfer: Ab Initio MO Studies of Isoelectronic Systems CH3O + CH2O and CH3NH2 + CH2NH2+

Ian H. Williams, Andrea B. Miller, Gerald M. Maggiora

Research output: Contribution to journalArticle

Abstract

The topography of the transition-state regions of the multidimensional potential energy surfaces for hydride transfer, (1) from methylamine to methaniminium and (2) from methoxide to formaldehyde, is described qualitatively on the basis of the characteristics (relative energies and curvatures) of critical points, each having negative curvature in the potential along the hydride-transfer reaction coordinate. Several new critical points on the HF/3-21G surfaces are reported. The geometry of hydride transfer depends upon steric effects, electrostatic interactions, and the possibility of 2e or 6e transition-state aromaticity. The varying interplay of these factors accounts for the differences between the reaction surfaces of the isoelectronic systems considered.

Original languageEnglish
Pages (from-to)530-537
Number of pages8
JournalJournal of the American Chemical Society
Volume112
Issue number2
DOIs
Publication statusPublished - 1 Jan 1990

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Reaction-Surface Topography for Hydride Transfer : Ab Initio MO Studies of Isoelectronic Systems CH3O + CH2O and CH3NH2 + CH2NH2+. / Williams, Ian H.; Miller, Andrea B.; Maggiora, Gerald M.

In: Journal of the American Chemical Society, Vol. 112, No. 2, 01.01.1990, p. 530-537.

Research output: Contribution to journalArticle

@article{71135450cdf546e99bb305a8d9ff97d6,
title = "Reaction-Surface Topography for Hydride Transfer: Ab Initio MO Studies of Isoelectronic Systems CH3O + CH2O and CH3NH2 + CH2NH2+",
abstract = "The topography of the transition-state regions of the multidimensional potential energy surfaces for hydride transfer, (1) from methylamine to methaniminium and (2) from methoxide to formaldehyde, is described qualitatively on the basis of the characteristics (relative energies and curvatures) of critical points, each having negative curvature in the potential along the hydride-transfer reaction coordinate. Several new critical points on the HF/3-21G surfaces are reported. The geometry of hydride transfer depends upon steric effects, electrostatic interactions, and the possibility of 2e or 6e transition-state aromaticity. The varying interplay of these factors accounts for the differences between the reaction surfaces of the isoelectronic systems considered.",
author = "Williams, {Ian H.} and Miller, {Andrea B.} and Maggiora, {Gerald M.}",
year = "1990",
month = "1",
day = "1",
doi = "10.1021/ja00158a009",
language = "English",
volume = "112",
pages = "530--537",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "2",

}

TY - JOUR

T1 - Reaction-Surface Topography for Hydride Transfer

T2 - Ab Initio MO Studies of Isoelectronic Systems CH3O + CH2O and CH3NH2 + CH2NH2+

AU - Williams, Ian H.

AU - Miller, Andrea B.

AU - Maggiora, Gerald M.

PY - 1990/1/1

Y1 - 1990/1/1

N2 - The topography of the transition-state regions of the multidimensional potential energy surfaces for hydride transfer, (1) from methylamine to methaniminium and (2) from methoxide to formaldehyde, is described qualitatively on the basis of the characteristics (relative energies and curvatures) of critical points, each having negative curvature in the potential along the hydride-transfer reaction coordinate. Several new critical points on the HF/3-21G surfaces are reported. The geometry of hydride transfer depends upon steric effects, electrostatic interactions, and the possibility of 2e or 6e transition-state aromaticity. The varying interplay of these factors accounts for the differences between the reaction surfaces of the isoelectronic systems considered.

AB - The topography of the transition-state regions of the multidimensional potential energy surfaces for hydride transfer, (1) from methylamine to methaniminium and (2) from methoxide to formaldehyde, is described qualitatively on the basis of the characteristics (relative energies and curvatures) of critical points, each having negative curvature in the potential along the hydride-transfer reaction coordinate. Several new critical points on the HF/3-21G surfaces are reported. The geometry of hydride transfer depends upon steric effects, electrostatic interactions, and the possibility of 2e or 6e transition-state aromaticity. The varying interplay of these factors accounts for the differences between the reaction surfaces of the isoelectronic systems considered.

UR - http://www.scopus.com/inward/record.url?scp=0025283987&partnerID=8YFLogxK

U2 - 10.1021/ja00158a009

DO - 10.1021/ja00158a009

M3 - Article

AN - SCOPUS:0025283987

VL - 112

SP - 530

EP - 537

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 2

ER -