The Ru/Sn heterobimetallic complexes CpRu(PPh3)(2)(SnCl3) (1), (Ind)Ru(PPh3)(2)(SnCl3) (2) and CpRu(TPPMS)(2)(SnCl3) (3) were studied as homogeneous catalysts for the electrooxidation of methanol to dimethoxymethane (DMM) and methyl formate (MF). Complexes 1, 2 and 3 exhibited significantly higher turnover numbers and current efficiencies than the corresponding mononuclear complexes CpRu(PPh3)(2)Cl (4) and CpRu(TPPMS)(2)Cl (5). The highest current efficiency (92.4%) and selectivity (100%) for DMM formation were obtained from the electrooxidation of methanol with complex 3. (C) 2004 Elsevier B.V. All rights reserved.