6533b833fe1ef96bd129b833
RESEARCH PRODUCT
Magnetoelectrochemical modulation of pre-organization processes in a 4,4′-dinitrobiphenyl azacrown macrocyclic lactam
María José AurellAntonio DoménechAna M. CosteroMaría-josé Bañulssubject
Reaction mechanismStereochemistryDihedral angleElectrochemistryReaction ratelcsh:ChemistryCrystallographychemistry.chemical_compoundElectron transferReaction rate constantchemistrylcsh:Industrial electrochemistrylcsh:QD1-999ElectrochemistryLactamCyclic voltammetrylcsh:TP250-261description
A magnetoelectrochemical effect consisting on the modulation of the reaction rate of pre-organization reactions in a 4,4′-dinitrobiphenyl azacrown lactam is described. The electrochemical response of that compound in DMSO solution at microelectrodes consists in two successive dinitrobiphenyl-centred one-electron transfer processes at −0.9 and −1.6 V vs. AgCl/Ag involving the transition from the dihedral geometry of the neutral starting compound to the planar geometry of the final dianion, resulting in an overall ECE mechanism. In the presence of moderate (0.05–0.2 T) static magnetic fields, the second electron transfer process decreases significantly, the apparent rate constant of the dihedral-planar pre-organization reaction being lowered from values of 6.2 s−1 to ca. 1.0 s−1. Keywords: Magnetoelectrochemistry, Azacrownlactams, Conformational pre-organization, Reaction rate
| year | journal | country | edition | language |
|---|---|---|---|---|
| 2004-09-01 | Electrochemistry Communications |