Solution-phase energy profiles for trigonal bipyramidal species postulated as intermediates for the hydrolysis of methyl ethylene phosphate

T. Uchimaru, S. Kawahara, S. Tsuzuki, Kazunari Matsumura, K. Taira

Research output: Contribution to journalArticle

4 Citations (Scopus)

Abstract

We present results of solution-phase ab initio and DFT investigations on the trigonal bipyramidal (TBP) intermediates postulated for the hydrolysis of methyl ethylene phosphate (MEP). A key intermediate for the hydrolysis would not be a TBP species with the hydroxyl group axial, but would be a TBP intermediate with the hydroxyl group equatorial. Considering the reaction pathways through this intermediate, not only exclusive ring opening in the dilute alkaline hydrolysis of MEP but also significant amount of exocyclic cleavage in the strong alkali can be rationalized. This interpretation is in accord with the mechanisms proposed by Lim et al. and by Lonnberg et al.

Original languageEnglish
Pages (from-to)215-221
Number of pages7
JournalJournal of Molecular Structure: THEOCHEM
Volume469
DOIs
Publication statusPublished - 1999 Sep 1
Externally publishedYes

Fingerprint

Propylene
hydrolysis
Hydrolysis
phosphates
Phosphates
ethylene
Hydroxyl Radical
profiles
Alkalies
Discrete Fourier transforms
energy
cleavage
alkalies
rings

Keywords

  • Ab initio and DFT calculations
  • Hydrolysis of methyl ethylene phosphate
  • Pseudorotation
  • Solution-phase reaction profile

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Computational Theory and Mathematics
  • Atomic and Molecular Physics, and Optics

Cite this

Solution-phase energy profiles for trigonal bipyramidal species postulated as intermediates for the hydrolysis of methyl ethylene phosphate. / Uchimaru, T.; Kawahara, S.; Tsuzuki, S.; Matsumura, Kazunari; Taira, K.

In: Journal of Molecular Structure: THEOCHEM, Vol. 469, 01.09.1999, p. 215-221.

Research output: Contribution to journalArticle

@article{68d5a8a1024748c68633e4a4ba1513a9,
title = "Solution-phase energy profiles for trigonal bipyramidal species postulated as intermediates for the hydrolysis of methyl ethylene phosphate",
abstract = "We present results of solution-phase ab initio and DFT investigations on the trigonal bipyramidal (TBP) intermediates postulated for the hydrolysis of methyl ethylene phosphate (MEP). A key intermediate for the hydrolysis would not be a TBP species with the hydroxyl group axial, but would be a TBP intermediate with the hydroxyl group equatorial. Considering the reaction pathways through this intermediate, not only exclusive ring opening in the dilute alkaline hydrolysis of MEP but also significant amount of exocyclic cleavage in the strong alkali can be rationalized. This interpretation is in accord with the mechanisms proposed by Lim et al. and by Lonnberg et al.",
keywords = "Ab initio and DFT calculations, Hydrolysis of methyl ethylene phosphate, Pseudorotation, Solution-phase reaction profile",
author = "T. Uchimaru and S. Kawahara and S. Tsuzuki and Kazunari Matsumura and K. Taira",
year = "1999",
month = "9",
day = "1",
doi = "10.1016/S0166-1280(99)00072-X",
language = "English",
volume = "469",
pages = "215--221",
journal = "Computational and Theoretical Chemistry",
issn = "2210-271X",
publisher = "Elsevier BV",

}

TY - JOUR

T1 - Solution-phase energy profiles for trigonal bipyramidal species postulated as intermediates for the hydrolysis of methyl ethylene phosphate

AU - Uchimaru, T.

AU - Kawahara, S.

AU - Tsuzuki, S.

AU - Matsumura, Kazunari

AU - Taira, K.

PY - 1999/9/1

Y1 - 1999/9/1

N2 - We present results of solution-phase ab initio and DFT investigations on the trigonal bipyramidal (TBP) intermediates postulated for the hydrolysis of methyl ethylene phosphate (MEP). A key intermediate for the hydrolysis would not be a TBP species with the hydroxyl group axial, but would be a TBP intermediate with the hydroxyl group equatorial. Considering the reaction pathways through this intermediate, not only exclusive ring opening in the dilute alkaline hydrolysis of MEP but also significant amount of exocyclic cleavage in the strong alkali can be rationalized. This interpretation is in accord with the mechanisms proposed by Lim et al. and by Lonnberg et al.

AB - We present results of solution-phase ab initio and DFT investigations on the trigonal bipyramidal (TBP) intermediates postulated for the hydrolysis of methyl ethylene phosphate (MEP). A key intermediate for the hydrolysis would not be a TBP species with the hydroxyl group axial, but would be a TBP intermediate with the hydroxyl group equatorial. Considering the reaction pathways through this intermediate, not only exclusive ring opening in the dilute alkaline hydrolysis of MEP but also significant amount of exocyclic cleavage in the strong alkali can be rationalized. This interpretation is in accord with the mechanisms proposed by Lim et al. and by Lonnberg et al.

KW - Ab initio and DFT calculations

KW - Hydrolysis of methyl ethylene phosphate

KW - Pseudorotation

KW - Solution-phase reaction profile

UR - http://www.scopus.com/inward/record.url?scp=0033198357&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0033198357&partnerID=8YFLogxK

U2 - 10.1016/S0166-1280(99)00072-X

DO - 10.1016/S0166-1280(99)00072-X

M3 - Article

VL - 469

SP - 215

EP - 221

JO - Computational and Theoretical Chemistry

JF - Computational and Theoretical Chemistry

SN - 2210-271X

ER -