Correlation of Polarographic Walf-Wave Potentials With Nuclear Magnetic Resonance "Chemical Shifts." Parallel Correlation With Chemical Reactivity Parameters. Report No. 35

Since nuclear magnetic resonance ''chemical shifts'' are considered to be good measures of electron densities in molecules, the extent to which they can be correlated with the polarographic half-wave potentials of organic compounds has been surveyed. To extend the applicability and interpretation of the proposed correlation, parallel correlatioan of E, with Hammett's sigma and Taft's sigma parameters were made, since both of the latter are also regarded as indication of electronic distrinution at the reactive center. The data in general support the view that changes in half-wave potential with structure are due to both electronic and steric effects, as well as perhaps to adsorption phenomena. Significantly, NMR data obtained with one type of substituent could be correlated with E/sub 1/2 data for a similar type of substituent. New NMR data for aliphatic nitro and halogen compounds are reported. (auth