Femtosecond Dynamics of the Methane - Methanol and Benzene - Phenol Conversions by an Iron - Oxo Species

Kazunari Yoshizawa, Yoshihito Shiota, Yoshihisa Kagawa, Tokio Yamabe

Research output: Contribution to journalArticle

38 Citations (Scopus)

Abstract

Femtosecond dynamic behavior of the methane - methanol conversion by the bare iron - oxo complex (FeO+) is presented using the B3LYP density-functional-theory (DFT) method. We propose that the reaction pathway for the direct methane - methanol conversion is partitioned into the H atom abstraction via a four-centered transition state and the methyl migration via a three-centered transition state. It is demonstrated that both the H atom abstraction and the methyl migration occur in a concerted manner in a time scale of 100 fs. The concerted H atom abstraction and the direct H atom abstraction via a transition state with a linear C - H O(Fe) array are compared. The direct H atom abstraction of methane is predicted to occur in a time scale of 50 fs. Isotope effects on the concerted and the direct H(D) atom abstractions are also computed and analyzed in the FeO+/methane system. Predicted values of the kinetic isotope effect (kH/kD) for the H(D) atom abstraction of methane are 9 in the concerted mechanism and 16 in the direct abstraction mechanism at 300 K. Dynamics calculations are also carried out on the benzene - phenol conversion by the FeO+ complex. The general profile of the electronic process of the benzene - phenol conversion is identical to that of the methane - methanol conversion with respect to essential bonding characters. It is demonstrated that the concerted H atom abstraction and the phenyl migration require 200 and 100 fs to be completed, respectively, in the FeO+/benzene system.

Original languageEnglish
Pages (from-to)2552-2561
Number of pages10
JournalJournal of Physical Chemistry A
Volume104
Issue number12
DOIs
Publication statusPublished - Mar 30 2000

Fingerprint

Methane
Phenol
Benzene
phenols
Methanol
methane
Iron
methyl alcohol
benzene
iron
Atoms
atoms
Isotopes
isotope effect
Density functional theory
density functional theory
Kinetics
kinetics
profiles
electronics

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry

Cite this

Femtosecond Dynamics of the Methane - Methanol and Benzene - Phenol Conversions by an Iron - Oxo Species. / Yoshizawa, Kazunari; Shiota, Yoshihito; Kagawa, Yoshihisa; Yamabe, Tokio.

In: Journal of Physical Chemistry A, Vol. 104, No. 12, 30.03.2000, p. 2552-2561.

Research output: Contribution to journalArticle

@article{3a6be6999e9d4f50a9095a6514a93db3,
title = "Femtosecond Dynamics of the Methane - Methanol and Benzene - Phenol Conversions by an Iron - Oxo Species",
abstract = "Femtosecond dynamic behavior of the methane - methanol conversion by the bare iron - oxo complex (FeO+) is presented using the B3LYP density-functional-theory (DFT) method. We propose that the reaction pathway for the direct methane - methanol conversion is partitioned into the H atom abstraction via a four-centered transition state and the methyl migration via a three-centered transition state. It is demonstrated that both the H atom abstraction and the methyl migration occur in a concerted manner in a time scale of 100 fs. The concerted H atom abstraction and the direct H atom abstraction via a transition state with a linear C - H O(Fe) array are compared. The direct H atom abstraction of methane is predicted to occur in a time scale of 50 fs. Isotope effects on the concerted and the direct H(D) atom abstractions are also computed and analyzed in the FeO+/methane system. Predicted values of the kinetic isotope effect (kH/kD) for the H(D) atom abstraction of methane are 9 in the concerted mechanism and 16 in the direct abstraction mechanism at 300 K. Dynamics calculations are also carried out on the benzene - phenol conversion by the FeO+ complex. The general profile of the electronic process of the benzene - phenol conversion is identical to that of the methane - methanol conversion with respect to essential bonding characters. It is demonstrated that the concerted H atom abstraction and the phenyl migration require 200 and 100 fs to be completed, respectively, in the FeO+/benzene system.",
author = "Kazunari Yoshizawa and Yoshihito Shiota and Yoshihisa Kagawa and Tokio Yamabe",
year = "2000",
month = "3",
day = "30",
doi = "10.1021/jp992464t",
language = "English",
volume = "104",
pages = "2552--2561",
journal = "Journal of Physical Chemistry A",
issn = "1089-5639",
publisher = "ACS Publications",
number = "12",

}

TY - JOUR

T1 - Femtosecond Dynamics of the Methane - Methanol and Benzene - Phenol Conversions by an Iron - Oxo Species

AU - Yoshizawa, Kazunari

AU - Shiota, Yoshihito

AU - Kagawa, Yoshihisa

AU - Yamabe, Tokio

PY - 2000/3/30

Y1 - 2000/3/30

N2 - Femtosecond dynamic behavior of the methane - methanol conversion by the bare iron - oxo complex (FeO+) is presented using the B3LYP density-functional-theory (DFT) method. We propose that the reaction pathway for the direct methane - methanol conversion is partitioned into the H atom abstraction via a four-centered transition state and the methyl migration via a three-centered transition state. It is demonstrated that both the H atom abstraction and the methyl migration occur in a concerted manner in a time scale of 100 fs. The concerted H atom abstraction and the direct H atom abstraction via a transition state with a linear C - H O(Fe) array are compared. The direct H atom abstraction of methane is predicted to occur in a time scale of 50 fs. Isotope effects on the concerted and the direct H(D) atom abstractions are also computed and analyzed in the FeO+/methane system. Predicted values of the kinetic isotope effect (kH/kD) for the H(D) atom abstraction of methane are 9 in the concerted mechanism and 16 in the direct abstraction mechanism at 300 K. Dynamics calculations are also carried out on the benzene - phenol conversion by the FeO+ complex. The general profile of the electronic process of the benzene - phenol conversion is identical to that of the methane - methanol conversion with respect to essential bonding characters. It is demonstrated that the concerted H atom abstraction and the phenyl migration require 200 and 100 fs to be completed, respectively, in the FeO+/benzene system.

AB - Femtosecond dynamic behavior of the methane - methanol conversion by the bare iron - oxo complex (FeO+) is presented using the B3LYP density-functional-theory (DFT) method. We propose that the reaction pathway for the direct methane - methanol conversion is partitioned into the H atom abstraction via a four-centered transition state and the methyl migration via a three-centered transition state. It is demonstrated that both the H atom abstraction and the methyl migration occur in a concerted manner in a time scale of 100 fs. The concerted H atom abstraction and the direct H atom abstraction via a transition state with a linear C - H O(Fe) array are compared. The direct H atom abstraction of methane is predicted to occur in a time scale of 50 fs. Isotope effects on the concerted and the direct H(D) atom abstractions are also computed and analyzed in the FeO+/methane system. Predicted values of the kinetic isotope effect (kH/kD) for the H(D) atom abstraction of methane are 9 in the concerted mechanism and 16 in the direct abstraction mechanism at 300 K. Dynamics calculations are also carried out on the benzene - phenol conversion by the FeO+ complex. The general profile of the electronic process of the benzene - phenol conversion is identical to that of the methane - methanol conversion with respect to essential bonding characters. It is demonstrated that the concerted H atom abstraction and the phenyl migration require 200 and 100 fs to be completed, respectively, in the FeO+/benzene system.

UR - http://www.scopus.com/inward/record.url?scp=0034732198&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0034732198&partnerID=8YFLogxK

U2 - 10.1021/jp992464t

DO - 10.1021/jp992464t

M3 - Article

AN - SCOPUS:0034732198

VL - 104

SP - 2552

EP - 2561

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

SN - 1089-5639

IS - 12

ER -