Vicinal Fluorine–Proton Coupling Constants: II. Individual Substituent Effects

The angular dependence and the effect of individual substituents upon the NMR vicinal fluorine–proton couplings3JFHhave been studied using data sets of experimental and calculated couplings. Coupling constants for a series of fluoroethane derivatives, CHXF–CH3and CH2F–CH2X(X= CH3, NH2, OH, and F), were calculated by means of the SCFab initioand semiempirical INDO/FPT methods. The calculated couplings reproduce correctly the main experimental trends in spite of the limitation in the calculation because of lack of electronic correlation and the use of medium size basis set. The individual substituent effects ΔKXiniare described by quadratic expressions on the relative electronegativities of substituents ΔχXi(ΔKXini=k0ni+kniΔχXi+ kniiΔχ2Xi). A selected data set of 58 experimental couplings, ranging from 1.9 to 44.4 Hz, has been collected from the literature. An extended Karplus equation with 16 coefficients that includes the electronegativity substituent effects has been derived from the experimental data set with a root-mean-square deviation of 1.2 Hz.