Isomers and isomerization reactions of four nitro derivatives of methane

Authors

  • Chaoyang Zhang,

    1. Department of Chemistry, Fudan University, Shanghai 200433, China
    2. Laboratory of Material Chemistry, Institute of Chemical Materials, China Academy of Engineering Physics (CAEP), P.O. Box 919-327, Mianyang, Sichuan 621900, China
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  • Xiaolin Wang,

    1. China Academy of Engineering Physics (CAEP), P.O. Box 919-1, Mianyang, Sichuan 621900, China
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  • Mingfei Zhou

    Corresponding author
    1. Department of Chemistry, Fudan University, Shanghai 200433, China
    • Department of Chemistry, Fudan University, Shanghai 200433, China
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Abstract

The nitro, nitrite, and aci-form isomers and the isomerization reactions of mono-, di-, tri-, and tetra-nitromethanes (NMs) were computationally investigated. The results show that the isomerization displacement of NO2 by ONO groups is surprisingly thermodynamically favored for the di-, tri-, and tetra-NMs. The molecular stability decreases and the isomerization becomes easier by increasing nitro groups. The largest attraction among substitutes takes place through the central carbon atom in C(ONO)4 and leads to its higher stability than the C(NO2)4 isomer. There is a concerted change of the CO[BOND]NO, C[BOND]ONO, and CON[BOND]O bonds in the nitrite isomers, that is, the weakened CO[BOND]NO bond is accompanied with the strengthened C[BOND]ONO and CON[BOND]O bonds, and vice versa. We only succeeded in finding two tight transition states of isomerization reactions from NO2 to ONO in the mono- and di-NMs, whereas isomerization reactions to the aci-forms through an intramolecular hydrogen transfer can always be found. © 2011 Wiley Periodicals, Inc. J Comput Chem 2011

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