Synthesis, characterization, and photochemical behavior of {Ru(arene)2+ derivatives of α-[PW11O39]7-:: An organometallic way to ruthenium-substituted heteropolytungstates

Reaction of [Ru(arene)Cl-2](2) (arene = benzene, toluene, p-cymene, hexamethylbenzene) with K-7[PW11O39]center dot 14H(2)O 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 infrared and multinuclear NMR (H-1, P-31, W-183) spectroscopies. The crystal structures of Na4K4[ [{PW11O39{Ru(benzene)112[WO2}]center dot 6H(2)O (NaK-2a-6H(2)O), K7H[{PW11O39{Ru(toluene)}}(2){WO2}]center dot 4H(2)O (K-2b-4H(2)O), and Cs3K2[PW11O39{Ru(p-cymene)(H2O)1]center dot 4H(2)O (CsK-1c-4H(2)O) 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, dimethyl sulfoxide, tetramethylene sulfoxide, and diphenyl sulfoxide) was investigated, and led to the formation Of [PW11O39{Ru(L)}](5-), in which the ruthenium is incorporated into the lacunary [PW11O39](7-) anion.