Theoretical Studies on the Conversion Mechanism Between Double-substituted Ammonium Oxides(R2HNO) and Double-substituted Hydroxylamines(R2NOH)——Electronegativity and Steric Effects of Substituents

Abstract

Abstract:

At the B3LYP/6-311++G(d,p) level, we studied the conversion mechanism between the double-substituted ammonium oxides(R₂HNO) and double-substituted hydroxylamines(R₂NOH) with R=NH₂, N(CH₃)₂, N(CH₂CH₃)₂, N[C(CH₃)₃]₂, OH, OCH₃, OCH₂CH₃ and OC(CH₃)₃. It was shown that the thermodynamic and kinetic stability of the double-substituted ammonium oxides R₂HNO are co-controlled by the electronegativity and steric effects. Amongst, the thermodynamic stability of amino-substituted species is dominated by steric effect, whereas that of the alkoxy-substituted species is dominated by electronegativity. The kinetic stability of both amino- and alkoxy-substituted species is mainly influenced by electronegativity.

Key words: R₂HNO, R₂NOH, Thermodynamic stability, Kinetic stability

TrendMD:

SHI Guo-Sheng, DING Yi-Hong*. Theoretical Studies on the Conversion Mechanism Between Double-substituted Ammonium Oxides(R₂HNO) and Double-substituted Hydroxylamines(R₂NOH)——Electronegativity and Steric Effects of Substituents[J]. Chem. J. Chinese Universities, 2009, 30(5): 1010.

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Theoretical Studies on the Conversion Mechanism Between Double-substituted Ammonium Oxides(R₂HNO) and Double-substituted Hydroxylamines(R₂NOH)——Electronegativity and Steric Effects of Substituents

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