A theoretical comparison of primary deuterium kinetic isotope effects in analogous hydride and hydron transfer processes

Ann E. Pain; Ian H. Williams

doi:10.1039/C39910001417

A theoretical comparison of primary deuterium kinetic isotope effects in analogous hydride and hydron transfer processes

Ann E. Pain, Ian H. Williams

Department of Chemistry

University of Bath

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

Abstract

The semiclassical primary deuterium kinetic isotope effect (3.30 at 298 K) for symmetrical hydride transfer from HN=CH₂ to HC≡NH ⁺, computed at the HF/3-21G level of ab initio molecular orbital (MO) theory, is smaller than that for analogous proton transfer from HN=CH ₂ to -HC=NH (4.38) owing to extensive participation in the reaction-coordinate vibrational mode of degrees of freedom other than asymmetric C⋯ H stretching.

Original language	English
Pages (from-to)	1417-1418
Number of pages	2
Journal	Journal of the Chemical Society, Chemical Communications
Volume	1991
Issue number	20
DOIs	https://doi.org/10.1039/C39910001417
Publication status	Published - 1 Dec 1991

ASJC Scopus subject areas

Molecular Medicine

Access to Document

10.1039/C39910001417

Cite this

@article{908a863ad2064cd8822782dcef02d84e,

title = "A theoretical comparison of primary deuterium kinetic isotope effects in analogous hydride and hydron transfer processes",

abstract = "The semiclassical primary deuterium kinetic isotope effect (3.30 at 298 K) for symmetrical hydride transfer from HN=CH2 to HC≡NH +, computed at the HF/3-21G level of ab initio molecular orbital (MO) theory, is smaller than that for analogous proton transfer from HN=CH 2 to -HC=NH (4.38) owing to extensive participation in the reaction-coordinate vibrational mode of degrees of freedom other than asymmetric C⋯ H stretching.",

author = "Pain, \{Ann E.\} and Williams, \{Ian H.\}",

year = "1991",

month = dec,

day = "1",

doi = "10.1039/C39910001417",

language = "English",

volume = "1991",

pages = "1417--1418",

journal = "Journal of the Chemical Society, Chemical Communications",

issn = "0022-4936",

publisher = "Chemical Society",

number = "20",

}

TY - JOUR

T1 - A theoretical comparison of primary deuterium kinetic isotope effects in analogous hydride and hydron transfer processes

AU - Pain, Ann E.

AU - Williams, Ian H.

PY - 1991/12/1

Y1 - 1991/12/1

N2 - The semiclassical primary deuterium kinetic isotope effect (3.30 at 298 K) for symmetrical hydride transfer from HN=CH2 to HC≡NH +, computed at the HF/3-21G level of ab initio molecular orbital (MO) theory, is smaller than that for analogous proton transfer from HN=CH 2 to -HC=NH (4.38) owing to extensive participation in the reaction-coordinate vibrational mode of degrees of freedom other than asymmetric C⋯ H stretching.

AB - The semiclassical primary deuterium kinetic isotope effect (3.30 at 298 K) for symmetrical hydride transfer from HN=CH2 to HC≡NH +, computed at the HF/3-21G level of ab initio molecular orbital (MO) theory, is smaller than that for analogous proton transfer from HN=CH 2 to -HC=NH (4.38) owing to extensive participation in the reaction-coordinate vibrational mode of degrees of freedom other than asymmetric C⋯ H stretching.

UR - https://www.scopus.com/pages/publications/0026045081

U2 - 10.1039/C39910001417

DO - 10.1039/C39910001417

M3 - Article

AN - SCOPUS:0026045081

SN - 0022-4936

VL - 1991

SP - 1417

EP - 1418

JO - Journal of the Chemical Society, Chemical Communications

JF - Journal of the Chemical Society, Chemical Communications

IS - 20

ER -

A theoretical comparison of primary deuterium kinetic isotope effects in analogous hydride and hydron transfer processes

Abstract

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Cite this