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Concerning the reaction between singlet nitrenium ions and water: A computational investigation on competitive reaction paths
Author(s) -
Facchini Paola,
Grandinetti Felice
Publication year - 2003
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.10182
Subject(s) - isomerization , chemistry , singlet state , dissociation (chemistry) , transition state , protonation , ion , exothermic reaction , reaction mechanism , ab initio , computational chemistry , ab initio quantum chemistry methods , medicinal chemistry , photochemistry , molecule , catalysis , organic chemistry , excited state , physics , nuclear physics
The reaction between singlet nitrenium ions XNH + (X = F and Cl) and H 2 O has been investigated by high‐level of theory ab initio calculations. The geometries of the involved intermediates, transition structures, and dissociation products have been optimized at the MP2(full)/6‐31G(d) level of theory, and accurate total energies have been obtained using the Gaussian‐3 (G3) procedure. The reaction commences by the exothermic formation of the FNHOH 2 +and ClNHOH 2 +intermediates, which are in turn able to undergo two distinct low‐energy reaction paths, namely, the isomerization to the N‐protonated isomers of the hydroxylamines FNHOH or ClNHOH, and the eventual extrusion of HF or HCl. The competitive or alternative occurrence of these two processes strictly depends on the nature of the substituent X. In the reaction between FNH + and H 2 O, the energy gained in the formation of the complex FNHOH 2 +from the association between FNH + and H 2 O, 52.1 kcal mol −1 , is by far larger than the activation barrier for the loss of HF from FNHOH 2 + , computed as 24.9 kcal mol −1 . In addition, the FNHOH 2 +intermediate requires 33.0 kcal mol −1 to overcome the barrier for the isomerization to FNH 2 OH + . Therefore, the reaction between FNH + and H 2 O is expected to occur practically exclusively by HF elimination with formation of the HNOH + ionic product. On the other hand, for the reaction between ClNH + and H 2 O, it is not possible to get a definitive conclusion on the competitive or alternative occurrence of the two reaction paths. In fact, the transition structure involved in the elimination of HCl from ClNHOH 2 +is only 3.4 kcal mol −1 lower in energy than the transition structure for the isomerization of ClNHOH 2 +to ClNH 2 OH + . In addition, the absolute values of the energy barriers of these two processes, 24.2 and 27.6 kcal mol −1 , respectively, are comparable with the energy gained in the formation of the complex ClNHOH 2 +from the association between ClNH + and H 2 O, 24.0 kcal mol − .1 Therefore, the ClNH + cation is predicted to react with water significantly slower than FNH + . © 2003 Wiley Periodicals, Inc. J Comput Chem 24: 547–564, 2003