Molecular orbital calculations of substituent effects on geminal coupling constants

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Abstract
The effect of substituents on H-H geminal coupling constants is discussed, within the framework of the Pople-Santry MO theory of nuclear spin coupling, but along lines different from those of the earlier treatment of Pople and Bothner-By. Expressions have been obtained for the effect of electron lone-pairs and of vacant non-bonding orbitals, the results for the latter case being important for interpretation of the effect of β substitution. These calculations have also been extended in an attempt to interpret the effect of lone-pairs and substituents, respectively, on N-H and C-H geminal coupling constants for systems like H2C = N- and H2C = CX-.