ChemInform Abstract: Evidence for a Square Scheme Involving Conformational Intermediates in Electron-Transfer Reactions of Copper(II)/(I) Systems.
Abstract
The cyclic voltammetric behavior of the complexes (Ia)/(Ib) and related systems is examined in details in both water and 80% MeOH in order to characterize the unusual electron-transfer behavior previously observed for this system and related complexes.
ChemInform Abstract
The cyclic voltammetric behavior of the complexes (Ia)/(Ib) and related systems is examined in details in both water and 80% MeOH in order to characterize the unusual electron-transfer behavior previously observed for this system and related complexes. The results are shown to be consistent with a square scheme in which two conformers of the complex ions exist. The values of the equilibrium and rate constants relating the two Cu(I) conformers (Ib) and the two Cu(II) conformers (Ia) are estimated for 25 °C. It is proposed that square schemes of this type exist for most Cu(II)/Cu(I) complexes and account for discrepancies previously observed in homogeneous cross-reaction electron-transfers involving both inorganic copper complexes and copper enzymes.
