INDO Molecular Orbital Calculations of Nuclear Spin–Spin Coupling Constants Over Three Bonds Between 13C and 1H in Some Simple Molecules

Molecular orbital calculations, at the INDO level, of the spin–spin coupling constants over three bonds between carbon-13 and protons are reported for a number of simple molecules. In propane the coupling depends on dihedral angle in the Karplus manner. Fluorine substituents cause changes in the computed coupling which are best described as alternating with the number of bonds intervening between the substituent and the coupled nuclei. Finer details of this phenomenon are discussed and calculations on propyllithium are performed. Replacement of a central carbon atom in propane by a heteroatom does not radically alter the computed couplings. The presence of a carbonyl group in the coupling path results in an overestimate of the magnitude of the coupling. In propene the coupling between 13C in position 1 and a methyl proton displays a maximum when the C—H bond of the methyl group lies parallel to the π orbitals. In toluene the coupling to a methyl proton is insensitive to the dihedral angle over half its range, a result of importance to structural studies. Among other molecules under consideration are methylacetylene, propionaldehyde, and the strained bicyclobutane. It is suggested that in certain instances the mean of the predictions from the INDO and CNDO/2 procedures may agree better with experiment than will the prediction from either procedure alone. Calculations on fluorobenzene and 1,2-difluorobenzene suggest that the main experimental trends of the couplings between carbon and protons within the benzene ring are reproduced. Such is perhaps not true for the five-membered heterocycles.