Internal Rotation of Methylcyclopropane and Related Molecules: Comparison of Experiment and Theory.

ABSTRACT

The internal rotation about the single bond connecting a cyclopropyl ring to a CH3, SiH3, GeH3, NH2, SH, or OH group was investigated. Both CCSD/cc-pVTZ and MP2/cc-pVTZ ab initio calculations were performed to predict the structures of these molecules and their internal rotation potential energy functions in terms of angles of rotation. The barriers to internal rotation for the CH3, SiH3, and GeH3 molecules from the calculations agree well with the experimental ones, within -11% to +1% for CCSD/cc-pVTZ and -4% to +9% for MP2/cc-pVTZ. Comparisons between theory and experiment were also performed for propylene oxide and propylene sulfide, and the agreements were very good. Theoretical calculations were performed to compute the internal rotation potential energy function for cyclopropanol, and these were used to guide the determination of a potential function based on experimental data. This molecule has two equivalent synclinal (gauche) conformers with an estimated barrier of 759 cm(-1) (9.1 kJ/mol) between them. The minima are at internal rotation angles of the OH group of 109° and 251°. The theoretical potential functions for cyclopropanethiol and cyclopropylamine were also calculated, and these agree reasonably well with previous experimental studies.