Résumé
Reaction of [Ru(arene)Cl2]2 (arene = benzene, toluene, p-cymene, hexamethylbenzene) with K7[PW11O39].14H2O provided two series of organometallic derivatives of heteropolytungstates: type-1 and type-2 complexes of general formulas [PW11O39{Ru(arene)(H2O)}]5- and [{PW11O39{Ru(arene)}}2{WO2}]8-, respectively. All compounds were characterized by IR and multinuclear NMR (1H, 31P, 183W) spectroscopies. The crystal structures of Na4K4[{PW11O39{Ru(benzene)}}2{WO2}].6H2O (NaK-2a.6H2O), K7H[{PW11O39{Ru(toluene)}}2{WO2}].4H2O (K-2b.4H2O), and Cs3K2[PW11O39{Ru(p-cymene)(H2O)}].4H2O (CsK-1c.4H2O) were obtained and revealed that the {Ru(arene)} fragment is supported on the oxometallic framework. Photochemical reactivity of [PW11O39{Ru(arene)(H2O)}]5- (arene = toluene, p-cymene) in the presence of various ligands L (L = H2O, DMSO, tetramethylene sulfoxide, and di-phenylsulfoxide) was investigated, and led to the formation of [PW11O39{Ru(L)}]5-, in which the ruthenium is incorporated into the lacunary [PW11O39]7- anion.