Barriers to Nitrogen Inversion in Cyclic and Acyclic Substituted Hydroxylamines. A Theoretical Study

Daniel Kost; Morton Raban

doi:10.1021/jo00872a017

Barriers to Nitrogen Inversion in Cyclic and Acyclic Substituted Hydroxylamines. A Theoretical Study

Daniel Kost, Morton Raban

Department of Chemistry

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

24 Scopus citations

Abstract

Approximate SCF-MO calculations (CNDO/2) have been used to study nitrogen inversion in N,N-dimethylhydroxylamine. The difference between the barriers in cyclic and acyclic substituted hydroxylamines was simulated by calculating the inversion barrier as a function of dihedral angle. Excellent agreement between calculated and experimental barriers was found. The results obtained have provided evidence for an inversion-dominated topomerization in dialkyl- and trialkylhydroxylamines and for rate retardation due to lone pair-lone pair interactions as well as the electronegativity of oxygen.

Original language	English
Pages (from-to)	1748-1751
Number of pages	4
Journal	Journal of Organic Chemistry
Volume	41
Issue number	10
DOIs	https://doi.org/10.1021/jo00872a017
State	Published - 1 May 1976

ASJC Scopus subject areas

Organic Chemistry

Access to Document

10.1021/jo00872a017

Cite this

@article{2fdae1fc250e458f8ea9f7ed69b865c2,

title = "Barriers to Nitrogen Inversion in Cyclic and Acyclic Substituted Hydroxylamines. A Theoretical Study",

abstract = "Approximate SCF-MO calculations (CNDO/2) have been used to study nitrogen inversion in N,N-dimethylhydroxylamine. The difference between the barriers in cyclic and acyclic substituted hydroxylamines was simulated by calculating the inversion barrier as a function of dihedral angle. Excellent agreement between calculated and experimental barriers was found. The results obtained have provided evidence for an inversion-dominated topomerization in dialkyl- and trialkylhydroxylamines and for rate retardation due to lone pair-lone pair interactions as well as the electronegativity of oxygen.",

author = "Daniel Kost and Morton Raban",

year = "1976",

month = may,

day = "1",

doi = "10.1021/jo00872a017",

language = "English",

volume = "41",

pages = "1748--1751",

journal = "Journal of Organic Chemistry",

issn = "0022-3263",

publisher = "American Chemical Society",

number = "10",

}

TY - JOUR

T1 - Barriers to Nitrogen Inversion in Cyclic and Acyclic Substituted Hydroxylamines. A Theoretical Study

AU - Kost, Daniel

AU - Raban, Morton

PY - 1976/5/1

Y1 - 1976/5/1

N2 - Approximate SCF-MO calculations (CNDO/2) have been used to study nitrogen inversion in N,N-dimethylhydroxylamine. The difference between the barriers in cyclic and acyclic substituted hydroxylamines was simulated by calculating the inversion barrier as a function of dihedral angle. Excellent agreement between calculated and experimental barriers was found. The results obtained have provided evidence for an inversion-dominated topomerization in dialkyl- and trialkylhydroxylamines and for rate retardation due to lone pair-lone pair interactions as well as the electronegativity of oxygen.

AB - Approximate SCF-MO calculations (CNDO/2) have been used to study nitrogen inversion in N,N-dimethylhydroxylamine. The difference between the barriers in cyclic and acyclic substituted hydroxylamines was simulated by calculating the inversion barrier as a function of dihedral angle. Excellent agreement between calculated and experimental barriers was found. The results obtained have provided evidence for an inversion-dominated topomerization in dialkyl- and trialkylhydroxylamines and for rate retardation due to lone pair-lone pair interactions as well as the electronegativity of oxygen.

UR - http://www.scopus.com/inward/record.url?scp=0000523705&partnerID=8YFLogxK

U2 - 10.1021/jo00872a017

DO - 10.1021/jo00872a017

M3 - Article

AN - SCOPUS:0000523705

SN - 0022-3263

VL - 41

SP - 1748

EP - 1751

JO - Journal of Organic Chemistry

JF - Journal of Organic Chemistry

IS - 10

ER -

Barriers to Nitrogen Inversion in Cyclic and Acyclic Substituted Hydroxylamines. A Theoretical Study

Abstract

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Cite this