Abstract
Density-functional-theory calculational results on the reaction pathway for alkane hydroxylation by a compound I model of cytochrome P450 are discussed. Our calculations demonstrate that the transition state for the H-atom abstraction of ethane involves a linear (Fe)O···H···C array and that the resultant carbon radical is bound to the iron-hydroxo species. This comptational result is partly consistent with the oxygen rebound mechanism in that the direct H-atom abstraction by the iron-oxo species takes place in the initial stages of the reaction pathway. However, the iron-hydroxo species cannot be viewed as a stable reaction intermediate in view of the energy diagram. Our results may not be consistent with the model of a free radical species with a finite lifetime and barrier to displacement of the OH group from the iron center that is commonly assumed and typically stated for the oxygen rebound mechanism.
| Original language | English |
|---|---|
| Pages (from-to) | 2669-2673 |
| Number of pages | 5 |
| Journal | Bulletin of the Chemical Society of Japan |
| Volume | 73 |
| Issue number | 12 |
| DOIs | |
| Publication status | Published - Dec 1 2000 |
| Externally published | Yes |
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All Science Journal Classification (ASJC) codes
- Chemistry(all)
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Energetics for the oxygen rebound mechanism of alkane hydroxylation by the iron-oxo species of cytochrome P450. / Yoshizawa, Kazunari; Shiota, Yoshihito; Kagawa, Y.
In: Bulletin of the Chemical Society of Japan, Vol. 73, No. 12, 01.12.2000, p. 2669-2673.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Energetics for the oxygen rebound mechanism of alkane hydroxylation by the iron-oxo species of cytochrome P450
AU - Yoshizawa, Kazunari
AU - Shiota, Yoshihito
AU - Kagawa, Y.
PY - 2000/12/1
Y1 - 2000/12/1
N2 - Density-functional-theory calculational results on the reaction pathway for alkane hydroxylation by a compound I model of cytochrome P450 are discussed. Our calculations demonstrate that the transition state for the H-atom abstraction of ethane involves a linear (Fe)O···H···C array and that the resultant carbon radical is bound to the iron-hydroxo species. This comptational result is partly consistent with the oxygen rebound mechanism in that the direct H-atom abstraction by the iron-oxo species takes place in the initial stages of the reaction pathway. However, the iron-hydroxo species cannot be viewed as a stable reaction intermediate in view of the energy diagram. Our results may not be consistent with the model of a free radical species with a finite lifetime and barrier to displacement of the OH group from the iron center that is commonly assumed and typically stated for the oxygen rebound mechanism.
AB - Density-functional-theory calculational results on the reaction pathway for alkane hydroxylation by a compound I model of cytochrome P450 are discussed. Our calculations demonstrate that the transition state for the H-atom abstraction of ethane involves a linear (Fe)O···H···C array and that the resultant carbon radical is bound to the iron-hydroxo species. This comptational result is partly consistent with the oxygen rebound mechanism in that the direct H-atom abstraction by the iron-oxo species takes place in the initial stages of the reaction pathway. However, the iron-hydroxo species cannot be viewed as a stable reaction intermediate in view of the energy diagram. Our results may not be consistent with the model of a free radical species with a finite lifetime and barrier to displacement of the OH group from the iron center that is commonly assumed and typically stated for the oxygen rebound mechanism.
UR - http://www.scopus.com/inward/record.url?scp=0034351755&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=0034351755&partnerID=8YFLogxK
U2 - 10.1246/bcsj.73.2669
DO - 10.1246/bcsj.73.2669
M3 - Article
AN - SCOPUS:0034351755
VL - 73
SP - 2669
EP - 2673
JO - Bulletin of the Chemical Society of Japan
JF - Bulletin of the Chemical Society of Japan
SN - 0009-2673
IS - 12
ER -