The reducing properties of highly delocalized radical anions and dianions of 1,2-di(hetero)arylethenes were investigated by theoretical calculations at the PBE0/6-311+G(d,p)/IEFPCM level. The results correlated nicely with the reduction potentials determined by analysis of the voltammetric curves for the reduction of the parent alkenes, and this allowed a reliable scale for their relative reducing strength to be established. In full agreement with calculations and electrochemical results, use of the appropriate 1,2-dipyridyl-1,2-disodioethane as a base led to the successful α-alkylation of bromophenylacetic acids under mild reaction conditions, thus avoiding the competitive reductive cleavage of aromatic C-Br bonds.

Reducing properties of 1,2-dipyridyl-1,2-disodioethanes: Chemical validation of theoretical and electrochemical predictions

MOCCI, FRANCESCA;
2016

Abstract

The reducing properties of highly delocalized radical anions and dianions of 1,2-di(hetero)arylethenes were investigated by theoretical calculations at the PBE0/6-311+G(d,p)/IEFPCM level. The results correlated nicely with the reduction potentials determined by analysis of the voltammetric curves for the reduction of the parent alkenes, and this allowed a reliable scale for their relative reducing strength to be established. In full agreement with calculations and electrochemical results, use of the appropriate 1,2-dipyridyl-1,2-disodioethane as a base led to the successful α-alkylation of bromophenylacetic acids under mild reaction conditions, thus avoiding the competitive reductive cleavage of aromatic C-Br bonds.
ANION-RADICALS; ELECTRON-AFFINITIES; REDUCTION; ACIDS; 1,2-DIARYL-1,2-DISODIOETHANES; TETRAHYDROFURAN; SOLVATION; DIANIONS
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Descrizione: RSC ADVANCES 2016 - Reducing properties of 1,2-dipyridyl-1,2- disodioethanes: chemical validation of theoretical and electrochemical predictions
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/11584/216286
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