The effect of substitutents on the strain energies of small ring compounds.
The effect of substitutents on the strain energy (SE) of cyclic molecules is examined at the CBS, G2, and G2(MP2) levels of theory. Alkyl substitutents have a meaningful effect upon the SE of small ring compounds. gem-Dimethyl substitution lowers the strain energy of cyclopropanes, cyclobutanes, epoxides, and dimethyldioxirane (DMDO) by 6-10 kcal/mol relative to an unbranched acyclic reference molecule. The choice of the reference compound is especially important for geminal electronegative substitutents. The SE of 1,1-difluorocyclopropane is estimated to be 20.5 kcal/mol relative to acyclic reference molecule 1,3-difluoropropane but is 40.7 kcal/mol with respect to the thermodynamically more stable (DeltaE = -20.2 kcal/mol) isomeric reference compound 2,2-difluoropropane. The SE of dioxirane (DO) is estimated to be approximately 18 kcal/mol while the SE of DMDO is predicted to be approximately equal to 11 kcal/mol by using homodesmotic reactions that maintain a balanced group equivalency. The total energy (CBS-APNO) of DMDO is 2.6 kcal/mol lower than that of isomeric 1,2-dioxacyclopentane that has an estimated SE of 5 kcal/mol. The thermodynamic stability of DMDO is a consequence of its relatively strong C-H (BDE = 102.7 kcal/mol) and C-CH(3) (BDE = 98.9 kcal/mol) bonds. By comparison, the calculated sec-C-H and -C-CH(3) G2 bond dissociation energies in propane are 100.3 and 90.5 kcal/mol.
Bach
Robert D
RD
Department of Chemistry and Biochemistry, University of Delaware, Newark, DE 19716, USA. rbach@udel.edu
Dmitrenko
Olga
O