Interplay of cubic building blocks in (et6-arene)ruthenium-containing tungsten and molybdenum oxides.
A series of molybdenum and tungsten organometallic oxides containing [Ru(arene)]2+ units (arene =p-cymene, C6Me6) was obtained by condensation of [[Ru(arene)Cl2]2] with oxomolybdates and oxotungstates in aqueous or nonaqueous solvents. The crystal structures of [[Ru(eta6-C6Me6]]4W4O16], [[Ru(eta6-p-MeC6H4iPr]]4W2O10], [[[Ru-(eta6-p-MeC6H4iPr)]2(mu-OH)3]2][[Ru(eta6-p-MeC6H4iPr)]2W8O28(OH)2[Ru(eta6-p-MeC6H4iPr)(H2O)]2], and [[Ru(eta6-C6Me6)]2M5O18[Ru(eta6-C6Me6)(H2O)]] (M = Mo, W) have been determined. While the windmill-type clusters [[Ru(eta6-arene)]4(MO3)4(mu3-O)4] (M = Mo, W; arene =p-MeC6H4iPr, C6Me6), the face-sharing double cubane-type cluster [[Ru(eta6-p-MeC6H4iPr)]4(WO2)2(mu3-O)4(mu4-O)2], and the dimeric cluster [[Ru(eta6-p-MeC6H4iPr)(WO3)3(mu3-O)3(mu3-OH)Ru(eta6-pMeC6H4iPr)(H2O)]2(mu-WO2)2]2- are based on cubane-like units, [(Ru(eta6-C6Me6)]2M5O18[Ru(eta6-C6Me6)(H2O)]] (M = Mo, W) are more properly described as lacunary Lindqvist-type polyoxoanions supporting three ruthenium centers. Precubane clusters [[Ru(eta6-arene)](MO3)2(mu-O)3(mu3-O)]6- are possible intermediates in the formation of these clusters. The cluster structures are retained in solution, except for [[Ru(eta6-p-MeC6H4iPr)]4Mo4O16], which isomerizes to the triple-cubane form.
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Laboratoire de Chimie Inorganique et Matériaux Moléculaires, Unité CNRS 7071, Université Pierre et Marie Curie, Paris, France.
Proust
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Herson
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Gouzerh
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