Repozytorium
Wyszukaj
Kolekcje
Inne
Understanding the molecular mechanism of the 1,3-dipolar cycloaddition between fulminic acid and acetylene in terms of the electron localization function and catastrophe theory.
Autorzy
Rok wydania
2004
Czasopismo
Numer woluminu
10
Strony
5165-5172
DOI
10.1002/chem.200400161
Kolekcja
Język
Angielski
Typ publikacji
Artykuł
The potential-energy profile of the 1,3-dipolar cycloaddition of fulminic acid and ethyne has been investigated theoretically within the framework provided by the electron localization function (ELF) analysis. This has been achieved by carrying out density functional theory (B3 LYP approach) calculations using the bonding evolution theory. Eight different domains of structural stability have been identified along the reaction path, as well as the bifurcation catastrophes responsible for the changes in the topology of the system. The analysis provides a chemical description of the reaction mechanism in terms of heterolytic concerted nonsynchronous bond formation: the first four catastrophes enable the simultaneous formation of the C-C bond and a lone pair on the nitrogen atom, whereas the remaining ones lead to the ring closure. The valence basin populations calculated along the reaction path do not support any mechanism involving pentavalent nitrogen. The simulation of the solvent effect, by means of a continuum model, does not indicate any significant difference of the mechanism of reaction between the gas phase and solution.
Adres publiczny
http://doi.org./ 10.1002/chem.200400161
Strona internetowa wydawcy
Podobne publikacje
The joint use of catastrophe theory and electron localization function to characterize molecular mechanisms. A density functional study of the Diels-Alder reaction between ethylene and 1,3-butadiene.
Berski Sławomir, Andrés Juan, Silvi Bernard, Domingo Luis R.
Olefin epoxidation by molybdenum peroxo compound : molecular mechanism characterized by the electron localization function and catastrophe theory.
Berski Sławomir, Sensato F., Polo Victor, Andrés Juan, Safont V. S.