Trisubstituted geminal diazaalkene derived transient 1,2-carbodications

Abstract

The coulombic repulsion between two adjacent cation centres of 1,2-carbodications is known to decrease with π- and/or n-donor substituents by a positive charge delocalization. Here we report the delocalization of the positive charge of transient 1,2-carbodications having one H-substituent by an intramolecular base-coordination. N-heterocyclic olefin (NHO) derived 2-pyrrolidinyl appended trisubstituted geminal diazaalkenes were used for the generation of transient 1,2-carbodications through a 2-e chemical oxidation process. We have also studied the 1-e oxidation reaction of trisubstituted geminal diazaalkenes (electrochemically and chemically) and also studied them using in situ EPR spectroscopy.