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Binuclear ruthenium(III) complexes containing a binucleating Schiff base ligand, L and Ph3P or Ph3As, [RuX2(EPh3)2]2L (X = Cl or Br; E = P or As) have been prepared by reacting [RuCl3(PPh3)3], [RuCl3(AsPh3)3], [RuBr3(AsPh3)3] and [RuBr3(PPh3)2(MeOH)] with Schiff bases in a 2:1 molar ratio. The Schiff bases used in this study were prepared by condensing the appropriate diamine with salicylaldehyde or benzoylacetone in a 1:2 molar ratio respectively. The complexes were characterised by analytical, spectral (i.r., electronic, e.p.r.) and electrochemical data. An octahedral structure has been proposed for all the new ligand-bridged binuclear RuIII complexes. The new complexes have been used as catalysts in aryl–aryl couplings and also subjected to antifungal activity studies.