|Gas-phase non-identity S(N)2 reactions at neutral nitrogen: a hybrid DFT study|
; Ren, Y
; Zhu, HJ
; Chu, SY
|发表期刊||INTERNATIONAL JOURNAL OF MASS SPECTROMETRY
|摘要||The gas-phase non-identity nucleophilic substitution reactions at saturated nitrogen Y-+ NH2X --> NH2Y + X- (Y, X = F, Cl, Br and I) were evaluated at the level of MPW1K/6-31+G(d, p). The enthalpies of reactions are exothermic only when the nucleophile is the lighter halide. Central barriers (DeltaH(YX)(not equal)) for reactions in the exothermic direction are slightly higher than the corresponding barriers at carbon. The lower overall barriers relative to the reactants (DeltaH(YX)(b)) than the corresponding reactions at carbon suggest that S(N)2 reactions at nitrogen may be more facile than at carbon. Both the central barriers (AH(YX)(not equal)) and the overall barriers (DeltaH(YX)(b)) correlate well with reaction exothermicity. Further interesting features of the non-identity reactions at nitrogen are the reasonable correlation between the central barriers (DeltaH(YX)(not equal)) with the composite geometrical looseness (%L-not equal), geometrical asymmetry (%AS(not equal)), and charge asymmetry of the transition structures (Deltaq (X - Y)). The data for the central barriers and the overall barriers show good agreement with the prediction of the Marcus equation and its modification, respectively. Kinetic and thermodynamic investigations predict that the nucleophilicity of X- in the S(N)2 at nitrogen decreases in the order F- < Cl- < Br- < I-, the leaving-group ability increases in the order F > Cl > Br > I. (C) 2003 Elsevier B.V. All rights reserved.|
|关键词||s(n)2 At Neutral Nitrogen
Hybrid Dft Method
|学科领域||Physics, Atomic, Molecular & Chemical
Yang, J,Ren, Y,Zhu, HJ,et al. Gas-phase non-identity S(N)2 reactions at neutral nitrogen: a hybrid DFT study[J]. INTERNATIONAL JOURNAL OF MASS SPECTROMETRY,2003,229(3):199-208.
Yang, J,Ren, Y,Zhu, HJ,&Chu, SY.(2003).Gas-phase non-identity S(N)2 reactions at neutral nitrogen: a hybrid DFT study.INTERNATIONAL JOURNAL OF MASS SPECTROMETRY,229(3),199-208.
Yang, J,et al."Gas-phase non-identity S(N)2 reactions at neutral nitrogen: a hybrid DFT study".INTERNATIONAL JOURNAL OF MASS SPECTROMETRY 229.3(2003):199-208.