Enthalpies of formation and isomerization of cis‐ and trans‐decalin, and their oxa‐analogs by G3(MP2)//B3LYP calculations

Abstract

AbstractG3(MP2)//B3LYP calculations have been carried out on trans‐ and cis‐decalin, and their mono‐, di‐, tri‐, and tetraoxa‐analogs. The main purpose of the work was to obtain enthalpies of formation for these compounds, and to study the relative stabilities of the cis–trans and positional isomers of the various (poly)oxadecalins. Comparison of the computational enthalpies of formation with the respective experimental ones, known only for the decalins and 1,3,5,7‐tetraoxadecalins, shows that in both cases the computational values are more negative than the experimental ones, the deviations being −5 to −7 kJ mol−1 for the decalins and −12 to −17 kJ mol−1 for the 1,3,5,7‐tetraoxadecalins. The respective computational enthalpies of cis–trans isomerization, however, are in excellent to satisfactory agreement with the experimental data. The cis–trans enthalpy differences vary from +11.0 kJ mol−1 for decalin to −15.4 kJ mol−1 for 1,4,5,8‐tetraoxadecalin. Low relative enthalpy values were also calculated for the cis isomers of 1,8‐dioxadecalin (−3.7 kJ mol−1), 1,3,6‐trioxadecalin (−4.6 kJ mol−1), 1,3,8‐trioxadecalin (−9.7 kJ mol−1), 1,4,5‐ trioxadecalin (−5.6 kJ mol−1), 1,3,5,8‐tetraoxadecalin (−7.3 kJ mol−1), and 1,3,6,8‐tetraoxadecalin (−14.5 kJ mol−1). Copyright © 2009 John Wiley & Sons, Ltd.