Abstract
High‐resolution 1H{14N} and proton‐coupled natural‐abundance 13C{14N} double resonance spectra have been recorded for pyridinium tetrafluoroborate dissolved in CD3CN. Iterative analysis of these spectra has provided the accurate values and relative signs of all possible long‐range 13C—1H coupling constants. These are compared with the respective values in pyridine and pyridine‐N‐oxide and discussed in terms of the relationship with the electronegativity of the N‐substituent. Experimental conditions allowing the observation of well‐resolved proton‐coupled 13C NMR spectra of charged heteroaromatics are also presented.

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