The palladium(II) dinuclear complex with bridging cyclometalated phosphines, P{Pd-2[mu-(C6H4)PPh2](2)(mu-O2CCH3)(2)} (Pd2L2), having a paddlewheel structure, is reversibly oxidized in CH2Cl2 to a dinuclear palladium(III) analogue via two successive one-electron steps. Solid state voltammetry of Pd2L2 in contact with aqueous electrolytes produce as one-electron oxidation with two competing mechanisms involving anion intercalation/anion binding between/to metal centres, chloride ions acting as inhibitors for the first pathway. R- and S-Pd2L2 produces a significant stereoselective electrocatalytic activity with respect to the oxidation of L- and D-glutamic acid in alkaline media. (C) 2007 Elsevier Ltd. All rights reserved.