Abstract
An extensive set of ground state ab initio and semiempirical molecular orbital calculations has been performed on both peroxytrifluoroacetic and peroxyacetic acids. The equilibrium geometry of peroxyacetic acid was calculated with the STO-3G and MINDO/3 methods, and peroxide rotational barriers for both peracids were obtained with STO-3G and PCILO. Extended basis set calculations with the 6-31G** basis were performed for both peracids to compare the electronic structures of these two compounds. Electrostatic potential maps in the region of the peroxide bonds of both peracids were also calculated using INDO wavefunetions. These results are discussed with respect to the enhanced reactivity of peroxytrifluoracetic acid relative to peroxyacetic acid and the nature of the oxygen electrophilicity in these compounds and by analogy in cytochrome P-450, for which peroxytrifluoroacetic acid is considered to be an effective chemical model.
| Original language | English (US) |
|---|---|
| Pages (from-to) | 1029-1036 |
| Number of pages | 8 |
| Journal | Tetrahedron |
| Volume | 33 |
| Issue number | 9 |
| DOIs | |
| State | Published - 1977 |
| Externally published | Yes |
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ASJC Scopus subject areas
- Biochemistry
- Organic Chemistry
- Drug Discovery
Cite this
The electronic structure of peracids. Functional models for cytochrome p-450. / Hjelmeland, Leonard M; Loew, G.
In: Tetrahedron, Vol. 33, No. 9, 1977, p. 1029-1036.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - The electronic structure of peracids. Functional models for cytochrome p-450
AU - Hjelmeland, Leonard M
AU - Loew, G.
PY - 1977
Y1 - 1977
N2 - An extensive set of ground state ab initio and semiempirical molecular orbital calculations has been performed on both peroxytrifluoroacetic and peroxyacetic acids. The equilibrium geometry of peroxyacetic acid was calculated with the STO-3G and MINDO/3 methods, and peroxide rotational barriers for both peracids were obtained with STO-3G and PCILO. Extended basis set calculations with the 6-31G** basis were performed for both peracids to compare the electronic structures of these two compounds. Electrostatic potential maps in the region of the peroxide bonds of both peracids were also calculated using INDO wavefunetions. These results are discussed with respect to the enhanced reactivity of peroxytrifluoracetic acid relative to peroxyacetic acid and the nature of the oxygen electrophilicity in these compounds and by analogy in cytochrome P-450, for which peroxytrifluoroacetic acid is considered to be an effective chemical model.
AB - An extensive set of ground state ab initio and semiempirical molecular orbital calculations has been performed on both peroxytrifluoroacetic and peroxyacetic acids. The equilibrium geometry of peroxyacetic acid was calculated with the STO-3G and MINDO/3 methods, and peroxide rotational barriers for both peracids were obtained with STO-3G and PCILO. Extended basis set calculations with the 6-31G** basis were performed for both peracids to compare the electronic structures of these two compounds. Electrostatic potential maps in the region of the peroxide bonds of both peracids were also calculated using INDO wavefunetions. These results are discussed with respect to the enhanced reactivity of peroxytrifluoracetic acid relative to peroxyacetic acid and the nature of the oxygen electrophilicity in these compounds and by analogy in cytochrome P-450, for which peroxytrifluoroacetic acid is considered to be an effective chemical model.
UR - http://www.scopus.com/inward/record.url?scp=0041771793&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=0041771793&partnerID=8YFLogxK
U2 - 10.1016/0040-4020(77)80221-4
DO - 10.1016/0040-4020(77)80221-4
M3 - Article
AN - SCOPUS:0041771793
VL - 33
SP - 1029
EP - 1036
JO - Tetrahedron
JF - Tetrahedron
SN - 0040-4020
IS - 9
ER -