Treatment of ruthenium complexes [CpRu(AN)(3)][PF6] (1a) (AN = acetonitrile) with iron complexes CpFe(CO)(2)X (2a-2c) (X = Cl, Br, I) and CpFe(CO)L'X (6a-6g) (L' = PMe3, PMe2Ph, PMePh2, PPh3, P(OPh)(3); X = Cl, Br, I) in refluxing CH2Cl2 for 3 h results in a triple ligand transfer reaction from iron to ruthenium to give stable ruthenium complexes CpRu(CO)(2)X (3a-3c) (X = Cl, Br, I) and CpRu(CO)L'X (7a-7g) (L' = PMe3, PMe2Ph, PMePh2, PPh3, P(OPh)(3); X = Br, I), respectively. Similar reaction of [CpRu(L)(AN)(2)][PF6] (1b: L = CO, 1c: P(OMe)(3)) causes double ligand transfer to yield complexes 3a-3c and 7a-7h. Halide on iron, CO on iron or ruthenium, and two acetonitrile ligands on ruthenium are essential for the present ligand transfer reaction. The dinuclear ruthenium complex 11a [CpRu(CO)(mu -I)](2) was isolated from the reaction of la with 6a at 0 degreesC. Complex 11a slowly decomposes in CH2Cl2 at room temperature to give 3a, and transforms into 7a by the reaction with PMe3. (C) 2000 Elsevier Science S.A. All rights reserved.