Abstract
The broken-symmetry (BS) and multideterminant approaches to atomic oxygen (O), molecular oxygen (O2) and iron-oxo (Fe(IV){double bond, long}O) core in P450 have elucidated electronic structures of the ground triplet and excited singlet states, which indicate isoelectronic characteristics of the species. The dissociation processes of the O-O and Fe-O double bonds are also examined to clarify the radical character, namely O-atom property responsible for radical mechanism of hydroxylations of alkanes and epoxidation of alkenes. This isolobal analogy has indeed enabled us to propose possible reaction mechanisms of oxygenation reactions by the Fe(IV){double bond, long}O species on the basis of available theoretical and experimental results for O and O2. Similarly, an isolobal analogy of the σ* bond among Fe(IV){double bond, long}O, dioxirane, peracids, etc. indicates the common electrophilic property for the oxygenation reactions. The small energy gaps between the high- and low-spin states of the transition structures and intermediates generated in the oxygenation reactions are found to be origins for spin crossover phenomena along the reaction pathways of these reactions.
| Original language | English |
|---|---|
| Pages (from-to) | 2044-2052 |
| Number of pages | 9 |
| Journal | Polyhedron |
| Volume | 28 |
| Issue number | 9-10 |
| DOIs | |
| Publication status | Published - Jun 22 2009 |
| Externally published | Yes |
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Keywords
- Broken-symmetry
- Fe(IV){double bond, long}O core
- Isoelectronic analogy
- Model Hamiltonian
- Multideterminants
- O
- O
- Spin crossover
ASJC Scopus subject areas
- Inorganic Chemistry
- Materials Chemistry
- Physical and Theoretical Chemistry
Cite this
Theory of chemical bonds in metalloenzymes XII : Electronic and spin structures of metallo-oxo and isoelectronic species and spin crossover phenomena in oxygenation reactions. / Yamaguchi, Kizashi; Shoji, Mitsuo; Isobe, Hiroshi; Yamanaka, Syusuke; Shimada, Jiro; Kitagawa, Yasutaka; Okumura, Mitsutaka.
In: Polyhedron, Vol. 28, No. 9-10, 22.06.2009, p. 2044-2052.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Theory of chemical bonds in metalloenzymes XII
T2 - Electronic and spin structures of metallo-oxo and isoelectronic species and spin crossover phenomena in oxygenation reactions
AU - Yamaguchi, Kizashi
AU - Shoji, Mitsuo
AU - Isobe, Hiroshi
AU - Yamanaka, Syusuke
AU - Shimada, Jiro
AU - Kitagawa, Yasutaka
AU - Okumura, Mitsutaka
PY - 2009/6/22
Y1 - 2009/6/22
N2 - The broken-symmetry (BS) and multideterminant approaches to atomic oxygen (O), molecular oxygen (O2) and iron-oxo (Fe(IV){double bond, long}O) core in P450 have elucidated electronic structures of the ground triplet and excited singlet states, which indicate isoelectronic characteristics of the species. The dissociation processes of the O-O and Fe-O double bonds are also examined to clarify the radical character, namely O-atom property responsible for radical mechanism of hydroxylations of alkanes and epoxidation of alkenes. This isolobal analogy has indeed enabled us to propose possible reaction mechanisms of oxygenation reactions by the Fe(IV){double bond, long}O species on the basis of available theoretical and experimental results for O and O2. Similarly, an isolobal analogy of the σ* bond among Fe(IV){double bond, long}O, dioxirane, peracids, etc. indicates the common electrophilic property for the oxygenation reactions. The small energy gaps between the high- and low-spin states of the transition structures and intermediates generated in the oxygenation reactions are found to be origins for spin crossover phenomena along the reaction pathways of these reactions.
AB - The broken-symmetry (BS) and multideterminant approaches to atomic oxygen (O), molecular oxygen (O2) and iron-oxo (Fe(IV){double bond, long}O) core in P450 have elucidated electronic structures of the ground triplet and excited singlet states, which indicate isoelectronic characteristics of the species. The dissociation processes of the O-O and Fe-O double bonds are also examined to clarify the radical character, namely O-atom property responsible for radical mechanism of hydroxylations of alkanes and epoxidation of alkenes. This isolobal analogy has indeed enabled us to propose possible reaction mechanisms of oxygenation reactions by the Fe(IV){double bond, long}O species on the basis of available theoretical and experimental results for O and O2. Similarly, an isolobal analogy of the σ* bond among Fe(IV){double bond, long}O, dioxirane, peracids, etc. indicates the common electrophilic property for the oxygenation reactions. The small energy gaps between the high- and low-spin states of the transition structures and intermediates generated in the oxygenation reactions are found to be origins for spin crossover phenomena along the reaction pathways of these reactions.
KW - Broken-symmetry
KW - Fe(IV){double bond, long}O core
KW - Isoelectronic analogy
KW - Model Hamiltonian
KW - Multideterminants
KW - O
KW - O
KW - Spin crossover
UR - http://www.scopus.com/inward/record.url?scp=66149190548&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=66149190548&partnerID=8YFLogxK
U2 - 10.1016/j.poly.2009.01.024
DO - 10.1016/j.poly.2009.01.024
M3 - Article
AN - SCOPUS:66149190548
VL - 28
SP - 2044
EP - 2052
JO - Polyhedron
JF - Polyhedron
SN - 0277-5387
IS - 9-10
ER -