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Volumn 120, Issue 4, 1998, Pages 775-783

Oxidation of alkenes, sulfides, amines, and phosphines with peroxynitrous acid: Comparison with other oxidants such as peroxyformic acid and dimethyldioxirane

Author keywords

[No Author keywords available]

Indexed keywords

ALKENE; AMINE; DIMETHYLDIOXIRANE; OXIDIZING AGENT; PEROXYFORMIC ACID; PEROXYNITRITE; PEROXYNITROUS ACID; PHOSPHINE DERIVATIVE; SULFIDE; UNCLASSIFIED DRUG;

EID: 0032481334     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja972518h     Document Type: Article
Times cited : (57)

References (77)
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    • 8d However, our calculations have shown that the corresponding RHF solution is triplet unstable and that further geometry optimizations of this transition structure at a correlated level (B3LYP, MP2, QCISD) reveal that it does not correspond to a stationary point,
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    • note
    • + for the B3LYP solution indicates that the triplet instability for this wave function is less than that for the RHF wave function.
  • 63
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    • note
    • 13a and, as a consequence, the calculated reaction barriers may be incorrect. Therefore, we recommend using the CISD optimized geometries provided that the barrier values are calculated at the QCISD(T) level.
  • 65
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    • note
    • (b) The relative rates of epoxidation of ethylene, propene, styrene, isobutene, and 2-butene with peracetic acid are 1, 22, 59, 484, and 489, respectively.
  • 67
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    • note
    • + = -0.084012 hartree).
  • 70
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    • note
    • 31
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    • note
    • 34b
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    • note
    • 1/2 = 1n 2/k); assuming a first-order rate constant for the O-O bond homolysis in peroxyformic acid and using the G2 calculated Gibbs free energy for the O-O bond cleavage (at 298 K).


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