Abstract
Alcohol oxidation by ferrate (FeO42-) in water is investigated from B3LYP density functional theory calculations in the framework of polarizable continuum model. The oxidizing power of three species, nonprotonated, monoprotonated, and diprotonated ferrates, was evaluated. The LUMO energy levels of nonprotonated and monoprotonated ferrates are greatly reduced by solvent effects, and as a result the oxidizing power of these two species is increased enough to effectively mediate a hydrogen-atom abstraction from the C-H and O-H bonds of methanol. The oxidizing power of these oxidants increases in the order nonprotonated ferrate < monoprotonated ferrate < diprotonated ferrate. The reaction pathway is initiated by C-H bond activation, followed by the formation of a hydroxymethyl radical intermediate or an organometallic intermediate with an Fe-C bond. Kinetic aspects of this reaction are analyzed from calculated energy profiles and experimentally known pK a values. The pH dependence of this reaction in water is explained well in terms of a multioxidant scheme.
| Original language | English |
|---|---|
| Pages (from-to) | 4380-4388 |
| Number of pages | 9 |
| Journal | Journal of Organic Chemistry |
| Volume | 70 |
| Issue number | 11 |
| DOIs | |
| Publication status | Published - May 27 2005 |
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All Science Journal Classification (ASJC) codes
- Organic Chemistry
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Participation of multioxidants in the pH dependence of the reactivity of ferrate(VI). / Kamachi, Takashi; Kouno, Tomohisa; Yoshizawa, Kazunari.
In: Journal of Organic Chemistry, Vol. 70, No. 11, 27.05.2005, p. 4380-4388.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Participation of multioxidants in the pH dependence of the reactivity of ferrate(VI)
AU - Kamachi, Takashi
AU - Kouno, Tomohisa
AU - Yoshizawa, Kazunari
PY - 2005/5/27
Y1 - 2005/5/27
N2 - Alcohol oxidation by ferrate (FeO42-) in water is investigated from B3LYP density functional theory calculations in the framework of polarizable continuum model. The oxidizing power of three species, nonprotonated, monoprotonated, and diprotonated ferrates, was evaluated. The LUMO energy levels of nonprotonated and monoprotonated ferrates are greatly reduced by solvent effects, and as a result the oxidizing power of these two species is increased enough to effectively mediate a hydrogen-atom abstraction from the C-H and O-H bonds of methanol. The oxidizing power of these oxidants increases in the order nonprotonated ferrate < monoprotonated ferrate < diprotonated ferrate. The reaction pathway is initiated by C-H bond activation, followed by the formation of a hydroxymethyl radical intermediate or an organometallic intermediate with an Fe-C bond. Kinetic aspects of this reaction are analyzed from calculated energy profiles and experimentally known pK a values. The pH dependence of this reaction in water is explained well in terms of a multioxidant scheme.
AB - Alcohol oxidation by ferrate (FeO42-) in water is investigated from B3LYP density functional theory calculations in the framework of polarizable continuum model. The oxidizing power of three species, nonprotonated, monoprotonated, and diprotonated ferrates, was evaluated. The LUMO energy levels of nonprotonated and monoprotonated ferrates are greatly reduced by solvent effects, and as a result the oxidizing power of these two species is increased enough to effectively mediate a hydrogen-atom abstraction from the C-H and O-H bonds of methanol. The oxidizing power of these oxidants increases in the order nonprotonated ferrate < monoprotonated ferrate < diprotonated ferrate. The reaction pathway is initiated by C-H bond activation, followed by the formation of a hydroxymethyl radical intermediate or an organometallic intermediate with an Fe-C bond. Kinetic aspects of this reaction are analyzed from calculated energy profiles and experimentally known pK a values. The pH dependence of this reaction in water is explained well in terms of a multioxidant scheme.
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U2 - 10.1021/jo050091o
DO - 10.1021/jo050091o
M3 - Article
VL - 70
SP - 4380
EP - 4388
JO - Journal of Organic Chemistry
JF - Journal of Organic Chemistry
SN - 0022-3263
IS - 11
ER -