Interplay of cubic building blocks in (eta(6)-arene)ruthenium-containing tungsten and molybdenum oxides

A series of molybdenum and tungsten organometallic oxides containing {Ru(ar ene)}(2+) units (arene=p-cymene, C6Me6) was obtained by condensation of [{R u(arene)Cl-2}(2)] with oxomolybdates and oxotungstates in aqueous or nonaqu eous solvents. The crystal structures of [{Ru(eta (6)-C6Me6)}(4)W4O16], [{R u(eta (6)-p-MeC(6)H(4)iPr)}(4)W2O10], [{[Ru-(eta (6)-p-MeC(6)H(4)iPr)](2)(m u -OH)(3)}(2)][{Ru(eta (6-)p-MeC(6)H(4)iPr)}(2)W8O28(OH)(2){Ru(eta (6)-p-Me -C(6)H(4)iPr)(H2O)}(2)], and [{Ru(eta (6)-C6Me6)}(2)M5O18{Ru(eta (6)-C6Me6) (H2O)}] (M=Mo, W) have been determined. While the windmill-type clusters [{ Ru(eta (6)-arene)}(4)(MO3)(4)(mu (3)-O)(4)] (M=Mo, W; arene=p-MeC(6)H(4)iPr , C6Me6), the face-sharing double cubane-type cluster [{Ru-(eta (6)-p-MeC(6 )H(4)iPr)}(4)(WO2)(2)(mu (3)-O)(4)(mu (4)-O)(2)], and the dimeric cluster [ {Ru(eta (6)-p-MeC(6)H(4)iPr)(WO3)(3)(mu (3)-O)(3)(mu (3)-OH)Ru(eta (6)-p-Me C(6)H(4)iPr)(H2O)}(2)(mu -WO2)(2)](2-) are based on cubane-like units, [{Ru (eta (6)-C6Me6)}(2)M5P18{Ru(eta (6)-C6Me6)(H2O)}] (M=Mo, W) are more proper ly described as lacunary Lindqvist-type polyoxoanions supporting three ruth enium centers. Precubane clusters [{Ru(eta (6)-arene)}(MO3)(2)(mu -O)(3)(mu (3)-O)](6-) are possible intermediates in the formation of these clusters: The cluster structures are retained in solution, except for [{Ru(eta (6)-p -MeC(6)H(4)iPr)}(4)Mo4O16], which isomerizes to the triple-cubane form.