Peptide complexes, self-exchange

Cu(III)(peptide)], with [Cu(I)(dmp)2], where dmp is 2,9-dimethyl-1,10-phen-anthroline, are rapid, outer-sphere processes which show some adherence to Marcus behavior,although the [Cu(dmp)2] self-exchange rate appears to be very dependent on the cross reaction,a lower limit of 3 X 10" mol" liter s arising from the [Cu(III)(peptide)] reactions, while a value of 9 x 10 mol liter s" is obtained from reaction with [IrCle], both at 25°C and 0.10 M ionic strength.Reactions of the copper(I) complex of the sterically hindered phenyl sulfonate derivative of dmp, [Cu(dpmp)2], with [Cu(III) (peptide)] are complicated by limiting rate behavior which is ascribed to activation of the copper(III) complex [reaction (25)]... 

Cross reactions of nickel(III)- and nickel(II)-peptide complexes conform readily to Marcus theory and are thought to be outer sphere but, in contrast to the copper system, give no unique self-exchange rate. Instead values range from 550 s for [Ni(III)/(II)(H 2Aib3)] through 1.3 x... 

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