The electronic structure of peracids. Functional models for cytochrome p-450

Research output: Contribution to journalArticle

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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 languageEnglish (US)
Pages (from-to)1029-1036
Number of pages8
JournalTetrahedron
Volume33
Issue number9
DOIs
StatePublished - 1977
Externally publishedYes

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Peracetic Acid
Cytochromes
Electronic structure
Peroxides
Chemical Models
Orbital calculations
Acids
Molecular orbitals
Static Electricity
Cytochrome P-450 Enzyme System
Ground state
Electrostatics
Oxygen
Geometry

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 journalArticle

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