The nuclear spin–spin coupling constants in methanol and methylamine: geometry and solvent effects Original Research Article

The effects of internal rotation and bond stretching on the spin–spin coupling constants in CH3OH and CH3NH2 have been calculated on MCSCF level. The reaction field theory has been used to simulate the effect of the water environment. The internal rotation causes considerable changes not only in 3JHH but in 1JCH and 2JOH (2JNH) as well. The coupling constants in the methyl group and some of the geminal couplings in polar moieties (2JOH, 2JNH and 2JHNH) exhibit a differential sensitivity to 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 3JHH. In the case of 1JCH and 2JHCH, 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 1JCO and 1JCN.