The nature of the transition structure for the oxidation of alkanes with dioxiranes

Journal of the American Chemical Society

Volumn 120, Issue 40, 1998, Pages 10528-10533

  Glukhovtsev, Mikhail N ^a   Canepa, Carlo ^a   Bach, Robert D ^a  

^a UNIVERSITY OF DELAWARE   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALKANE DERIVATIVE; DIOXIRANE DERIVATIVE; PEROXIDE; UNCLASSIFIED DRUG;

ARTICLE; EPOXIDATION; OXIDATION; REACTION ANALYSIS; THERMODYNAMICS;

EID: 0032517322     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja9813156     Document Type: Article

References (13)

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2. For reviews, see: (a) Adam, W.; Curci, R.; Edwards, J. O. Acc. Chem. Res. 1989, 22, 205. (b) Murray, R. W. Chem. Rev. 1989, 89, 1187. (c) Bunnelle, W. H. Chem. Rev. 1991, 91, 335 and references therein. (d) Adam, W.; Hadjiarapoglou, L. P.; Curci, R.; Mello, R. In Organic Peroxides; Ando, W.; Ed., Wiley: New York, 1992; p 195. (e) Curci, R.; Dinoi, A.; Rubino, M. F. Pure Appl. Chem. 1995, 67, 811.
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4. For reviews, see: (a) Adam, W.; Curci, R.; Edwards, J. O. Acc. Chem. Res. 1989, 22, 205. (b) Murray, R. W. Chem. Rev. 1989, 89, 1187. (c) Bunnelle, W. H. Chem. Rev. 1991, 91, 335 and references therein. (d) Adam, W.; Hadjiarapoglou, L. P.; Curci, R.; Mello, R. In Organic Peroxides; Ando, W.; Ed., Wiley: New York, 1992; p 195. (e) Curci, R.; Dinoi, A.; Rubino, M. F. Pure Appl. Chem. 1995, 67, 811.
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11. 14 calculations with the stable UB3LYP wave function lead to a decrease in energy only of 1.9 kcal/mol. This indicates that the RHF wave function is very close to the stability threshold. Our calculations on oxidation reactions with dioxiranes and peroxyformic and peroxynitrous acids have shown that in cases of an RHF → UHF wave function instability for transition structures when the energy gap between unstable RB3LYP and stable UB3LYP solutions is small, the activation barriers calculated at the QCISD(T)//B3LYP level are close to those computed at the QCISD(T)//QCISD level of theory.
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