Synthetic, spectral, electrochemical and structural aspects of some Ru(II) arene complexes with some novel bridging ligands

Abstract

Reactions of chloro-bridged dimeric Ru(II) complexes [{Ru(η⁶-arene)Cl₂}₂] with bridging ligands 1,4-dicyanamidobenzene, N,N′-dicyano 4-4′-diaminobiphenyl, 2,5-dichloro-1,4-dicyanamidobenzene and 2,5-dimethyl-1,4-dicyanamidobenzene (referred hereafter as dcdH₂, bpH₂, ddcl and dmcd) in dicloromethane at room temperature gave binuclear complexes with the general formulation [{Ru(η⁶-arene)Cl₂}₂(μ-L)]. However, reactions of these bridging ligands with the complexes [Ru(η⁶-arene)(P)Cl₂](η⁶-arene=benzene or p-cymene; P=PPh_3, PEt₃ or MePPrⁱ₂) in methanol, in presence of NH₄PF₆, gave cationic arene complexes [{Ru(η⁶-arene)(P)Cl}₂(L)]²⁺ (L=dcdH₂, bpH_2, dmcd or ddcl). The reaction products have been characterized by physico-chemical methods viz., elemental analyses, IR, ¹H-, ¹³C-, ³¹P-NMR, electronic and FAB mass spectra. The complexes under study are highly stable at room temperature. However, their solutions in coordinating solvents like acetonitrile or dimthylsulfoxide undergo substitution reactions to give substitutional products with the formulation RuCl₂(sol)₄. It has been confirmed by single crystal X-ray diffraction studies.