The effect of substituents on the deprotonation energy of selected primary, secondary and tertiary alcohols

J. Mestres, M. Duran, J. Bertrán, I. Csizmadia

Research output: Contribution to journalArticle

7 Citations (Scopus)

Abstract

Ab initio computations were carried out at the Hartree-Fock level of theory on primary, secondary and tertiary alcohols and also on their deprotonated conjugate bases containing methyl and phenyl substituents using a variety of basis sets (3-21G, 6-31G and triple-zeta) in combination with diffuse and polarization functions. The computed gas phase acidity as measured by the proton affinity of the conjugate bases (alkoxide ions) increased with increasing degree of substitution, in agreement with experimental gas phase acidity but in disagreement with experimental solution acidity trends. The molecular conformations, fundamental vibrational frequencies and charge distributions of selected alcohols and their conjugate bases were also studied.

Original languageEnglish
Pages (from-to)229-249
Number of pages21
JournalJournal of Molecular Structure: THEOCHEM
Volume358
Issue numberC
DOIs
Publication statusPublished - Dec 14 1995

Fingerprint

Deprotonation
Acidity
acidity
alcohols
Gases
Alcohols
Molecular Conformation
vapor phases
Protons
Charge distribution
frequency distribution
alkoxides
Vibrational spectra
Ions
charge distribution
affinity
Conformations
energy
Substitution reactions
substitutes

Keywords

  • Ab initio HF computation
  • Aliphatic and aromatic alcohols and their alkoxide ions
  • Gas phase acidity
  • Vibrational spectral data

ASJC Scopus subject areas

  • Biochemistry
  • Physical and Theoretical Chemistry
  • Condensed Matter Physics

Cite this

The effect of substituents on the deprotonation energy of selected primary, secondary and tertiary alcohols. / Mestres, J.; Duran, M.; Bertrán, J.; Csizmadia, I.

In: Journal of Molecular Structure: THEOCHEM, Vol. 358, No. C, 14.12.1995, p. 229-249.

Research output: Contribution to journalArticle

@article{ac264b6a43fe4b4a9e6b0079dc5902b3,
title = "The effect of substituents on the deprotonation energy of selected primary, secondary and tertiary alcohols",
abstract = "Ab initio computations were carried out at the Hartree-Fock level of theory on primary, secondary and tertiary alcohols and also on their deprotonated conjugate bases containing methyl and phenyl substituents using a variety of basis sets (3-21G, 6-31G and triple-zeta) in combination with diffuse and polarization functions. The computed gas phase acidity as measured by the proton affinity of the conjugate bases (alkoxide ions) increased with increasing degree of substitution, in agreement with experimental gas phase acidity but in disagreement with experimental solution acidity trends. The molecular conformations, fundamental vibrational frequencies and charge distributions of selected alcohols and their conjugate bases were also studied.",
keywords = "Ab initio HF computation, Aliphatic and aromatic alcohols and their alkoxide ions, Gas phase acidity, Vibrational spectral data",
author = "J. Mestres and M. Duran and J. Bertr{\'a}n and I. Csizmadia",
year = "1995",
month = "12",
day = "14",
doi = "10.1016/0166-1280(95)04353-5",
language = "English",
volume = "358",
pages = "229--249",
journal = "Computational and Theoretical Chemistry",
issn = "2210-271X",
publisher = "Elsevier BV",
number = "C",

}

TY - JOUR

T1 - The effect of substituents on the deprotonation energy of selected primary, secondary and tertiary alcohols

AU - Mestres, J.

AU - Duran, M.

AU - Bertrán, J.

AU - Csizmadia, I.

PY - 1995/12/14

Y1 - 1995/12/14

N2 - Ab initio computations were carried out at the Hartree-Fock level of theory on primary, secondary and tertiary alcohols and also on their deprotonated conjugate bases containing methyl and phenyl substituents using a variety of basis sets (3-21G, 6-31G and triple-zeta) in combination with diffuse and polarization functions. The computed gas phase acidity as measured by the proton affinity of the conjugate bases (alkoxide ions) increased with increasing degree of substitution, in agreement with experimental gas phase acidity but in disagreement with experimental solution acidity trends. The molecular conformations, fundamental vibrational frequencies and charge distributions of selected alcohols and their conjugate bases were also studied.

AB - Ab initio computations were carried out at the Hartree-Fock level of theory on primary, secondary and tertiary alcohols and also on their deprotonated conjugate bases containing methyl and phenyl substituents using a variety of basis sets (3-21G, 6-31G and triple-zeta) in combination with diffuse and polarization functions. The computed gas phase acidity as measured by the proton affinity of the conjugate bases (alkoxide ions) increased with increasing degree of substitution, in agreement with experimental gas phase acidity but in disagreement with experimental solution acidity trends. The molecular conformations, fundamental vibrational frequencies and charge distributions of selected alcohols and their conjugate bases were also studied.

KW - Ab initio HF computation

KW - Aliphatic and aromatic alcohols and their alkoxide ions

KW - Gas phase acidity

KW - Vibrational spectral data

UR - http://www.scopus.com/inward/record.url?scp=0000285784&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0000285784&partnerID=8YFLogxK

U2 - 10.1016/0166-1280(95)04353-5

DO - 10.1016/0166-1280(95)04353-5

M3 - Article

AN - SCOPUS:0000285784

VL - 358

SP - 229

EP - 249

JO - Computational and Theoretical Chemistry

JF - Computational and Theoretical Chemistry

SN - 2210-271X

IS - C

ER -