Trisubstituted Geminal Diazaalkenes Derived Transient 1,2-Carbodications

MANDAL, DEBDEEP; NEUMAN, NICOLÁS I; KUNDU, ABHINANDA; PATI, SWAPAN; JANA, ANUKUL; CHANDRA, SHUBHADEEP; DAS, SHUBHAJIT; RAWAT, HEMANT; SARKAR, BIPRAJIT; STEIN, FELIX; SARKAR, PALLAVI; SARKAR, ARIGHNA; CHANDRASEKHAR, VADAPALLI

CHEMICAL COMMUNICATIONS

ROYAL SOC CHEMISTRY

Lugar: CAMBRIDGE; Año: 2020

1359-7345

Coulombic repulsion between two adjacent cation centres of 1,2-carbodications are known to decrease with π- and/or n-donor substituents by the positive charge delocalization. Here we report the delocalization of 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 employed 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 by in situ EPR spectroscopy.