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Journal of Structural Chemistry

2010 year, number 6

A STUDY OF HYDROGEN BONDS IN p-SUBSTITUTED CALIX[4]- AND CALIX[6]ARENES BY AB INITIO AND ELECTRON DENSITY FUNCTIONAL METHODS

A. N. Novikov, Y. E. Shapiro
Keywords: p-substituted calixarene, p-halogenocalix[4]arene, p-halogenocalix[6]arene, hydrogen bond, Hartree-Fock method, electron density functional method, Hammett constants, multiple correlation, Grootenhuis et al. method
Pages: 1062-1072

Abstract

RHF/3-21G and B3LYP/3-21G methods are used to calculate the hydrogen bond energies in calix[4]-, calix[6]-, p-fluorocalix[4]-, p-fluorocalix[6]-, p-chlorocalix[4]-, p-chlorocalix[6]-, p-bromocalix[4]-, p-bromocalix[6]-, p-iodocalix[4]-, p-iodocalix[6]-arenes and a number of other p-substituted calix[4]- and calix[6]arenes (R = Me, OMe, NO2, Ac, NH2, CN, ). The calculations along with the structural data give evidence of the cooperative effect of hydrogen bonding. Multiple correlation (p ≥ 0.9) between the pairs of Hammett substituent constants and the calculated values of hydrogen bond energies in the corresponding p-substituted calixarenes is found. It is predicted that in the presence of weak bases and in aprotic solvents as well as in the gas phase, the nucleophilic substitution reaction involving p-halogen calix[6]arenes should proceed through diastereomeric transition states.