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A theoretical investigation on the cycloaddition reaction between azocarbenium ions and nitriles
Author(s) -
Li ZhiMing,
Wang QuanRui
Publication year - 2008
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.21560
Subject(s) - chemistry , cycloaddition , polarizable continuum model , coupled cluster , computational chemistry , cationic polymerization , ion , substituent , gas phase , density functional theory , activation barrier , polarizability , solvent effects , solvent , molecule , stereochemistry , organic chemistry , catalysis
The 1,3‐dipolar cycloaddition reactions of the cationic 1,3‐dipolarophiles of azocarbenium ion 1 with HCN in the gas phase were examined using the density functional theory, QCISD method (Quadratic configuration interaction using single and double substitutions) and CCSD(T) (Coupled cluster calculations with single and double excitations and a perturbative estimate of triple contributions calculations) calculations. The theoretical results revealed that the reaction takes place via an initial formation of a 1:1 complex of the two reactants, mainly driven by charge interaction, followed by an asynchronous concerted cyclization forming the 3 H ‐[1,2,4]‐triazolium ion 3, which undergo [1,2]‐H shift to provide the 1 H ‐[1,2,4]‐triazolium ion 4. The effect of the solvent has been modeled by using the isodensity‐surface polarizable continuum (IPCM) model and the calculation showed that the reaction in CH 2 Cl 2 solution proceeds in a similar manner as in gas phase with only a slight derivation of activation barrier. The substituent effects have also been investigated. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2008