The nuclear spin-coupling constants in methanol and methylamine: geometry and solvent effects

摘要

The effects of internal rotation and bond stretching on the spin-spin coupling constants in CH_3OH and CH_3NH_2 have been calculated on MCSCF level. The reaction fields theory has been used to simulate the effect of the water environment. The internal rotation causes considerable changes not only in ~3J_(HH) but in ~1J_(CH) and ~2J_(OH) (~2J_(NH)) as well. The coupling constants in the methyl group and some of the geminal couplings in polar moieties (~2J_(OH), ~2J_(NH) and ~2J_(HNH)) exhibit a differential sensitivity of bond length variations. This phenomenon does not emerge for the single bond couplings involving nuclei with lone pairs. The simulation of the aqueous environment leads to the conclusion that solvent effects are substantial for the single bond coupling constants and for some of the geminal coupling constants but negligible for ~3J_(HH). In the case of ~1J_(CH) and ~2J_(HCH), solvent effects depend considerably on the molecular conformation. All effects under study are dominated by the changes in the Fermi contact terms, with the exception of the internal rotation effects on ~1J_(CO) and ~1J_(CN).