The reaction of the ferrocene-containing bridging ligands 1,1'-bis(4-pyridylthio)ferrocene (1), 1',1"'-bis(4-pyridylthio)biferrocene (2), and 1',1"'-bis(diphenylphosphanyl)biferrocene (3), with the chloro-bridged dinuclear complexes [(p-cymene)RuCl(mu-Cl)](2) and [(CpMCl)-M-*(mu-Cl)](2) (M=Rh, Ir) affords trinuclear and tetranuclear metal complexes in good yields: [{(p-cymene)RuCl(mu-Cl)}(2)(mu-L)] (4: L = 1; 7: L = 2; 10: L = 3), [{(CpMCl)-M-*(mu-Cl)}(2)(mu-L)] (5: L = 1, M = Rh; 6: L = 1, M = Ir, 8: L = 2, M = Rh; 9: L = 2, M = Ir; 11: L = 3, M = Rh; 12: L = 3, M = Ir). The molecular structures of 3 and 5 have been determined by X-ray structure analysis. These complexes show quasi-reversible redox processes of the bridging ligands as well as irreversible redox processes of the terminal metal ions. Reaction of [{(CpMCl)-M-*(mu-Cl)}(2)(mu-1)] with AgPF6 affords [{((CpM)-M-*)(4)(mu-Cl)(4)}(mu-1)(2)](PF6)(4) (13: M = Rh, 14: M = Ir), which are chloro-bridged polynuclear complexes.
