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Interplay of Cubic Building Blocks in (#eta#~6-arene)Ruthenium-Containing Tungsten and Molybdenum Oxides

机译:(#eta#〜6-芳烃)含钌钨和钼氧化物中立方结构单元的相互作用

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摘要

A series of molybdenum and tungsten organometallic oxides containing {Ru(arene)}~(2+) units (arene=p-cymene, C_6Me_6) was obtained by condensation of [{Ru(arene)Cl_2}_2] with oxomolybdates and oxotungstates in aqueous or nonaqueous solvents. The crystal structures of [{Ru(#eta#~6-C_6Me_6)}_4W_4O_(16)], [{Ru(#eta#~6-p-MeC_6H_4iPr)}_4W_2O_(10)], [{[Ru(#eta#~6-p-MeC_6H_4iPr)]_2(#mu#-OH)_3}_2][{Ru(#eta#~6-p-MeC_6H_4iPr)}_2W_8O_(28)(OH)_2{Ru(#eta#~6-p-MeC_6H_4iPr)(H_2O)}_2], and [{Ru(#eta#~6-C_6Me_6)}_2M_5O_(18){Ru(#eta#~6-C_6Me_6)(H_2O)}] (M=Mo,W) have been determined. While the windmill-type clusters [{Ru(#eta#~6-arene)}_4(MO_3)_4(#mu#_3-O)_4](M=Mo, W; arene=p-MeC_6H_4iPr, C_6Me_6), the face-sharing double cubane-type cluster [{Ru(#eta#~6-p-MeC_6H_4iPr)}_4(WO_2)_2(#mu#_4-O)_2], and the dimeric cluster cluster [{Ru(#eta#~6-p-MeC_6H_4iPr)(WO_3)_3(#mu#_3-OH)Ru(#eta#~6-p-MeC_6H_4iPr)(H_2O)}_2(#mu#-WO_2)_2]~(2-) are based on cubane-like units, [{Ru(#eta#~6-C_6Me_6)}_2M_5O_(18){Ru(#eta#~6-C_6Me_6)(H_2O)}](M=Mo, W) are more properly described as lacunary Lindqvist-type polyoxo-anions supporting three ruthenium centers. Precubane clusters [{Ru(#eta#~6-arene)}(MO_3)_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_6H_4iPr)}_4Mo_4O_(16)], which isomerizes to the triple-cubane form.
机译:通过将[{Ru(arene)Cl_2} _2]与含氧钼酸盐和氧钨钨酸盐缩合,得到一系列含有{Ru(arene)}〜(2+)单元(芳烃=对伞花烃,C_6Me_6)的钼和钨有机金属氧化物。水性或非水性溶剂。 [{Ru(#eta#〜6-C_6Me_6)} _ 4W_4O_(16)],[{Ru(#eta#〜6-p-MeC_6H_4iPr)} _ 4W_2O_(10)],[{[Ru(# eta#〜6-p-MeC_6H_4iPr)] _ 2(#mu#-OH)_3} _2] [{Ru(#eta#〜6-p-MeC_6H_4iPr)} _ 2W_8O_(28)(OH)_2 {Ru(#eta #〜6-p-MeC_6H_4iPr)(H_2O)} _ 2]和[{Ru(#eta#〜6-C_6Me_6)} _ 2M_5O_(18){Ru(#eta#〜6-C_6Me_6)(H_2O)}]]( M = Mo,W)已确定。风车类型的簇[{Ru(#eta#〜6-arene)} _ 4(MO_3)_4(#mu#_3-O)_4](M = Mo,W; arene = p-MeC_6H_4iPr,C_6Me_6),共享脸部双重古巴型簇[{Ru(#eta#〜6-p-MeC_6H_4iPr)} _ 4(WO_2)_2(#mu#_4-O)_2]和二聚簇簇[{Ru(# eta#〜6-p-MeC_6H_4iPr)(WO_3)_3(#mu#_3-OH)Ru(#eta#〜6-p-MeC_6H_4iPr)(H_2O)} _ 2(#mu#-WO_2)_2]〜(2 -)基于类似古巴的单位,[{Ru(#eta#〜6-C_6Me_6)} _ 2M_5O_(18){Ru(#eta#〜6-C_6Me_6)(H_2O)}](M = Mo,W)可以更恰当地描述为支持三个钌中心的凹腔Lindqvist型多氧阴离子。 Precubane簇[{Ru(#eta#〜6-arene)}(MO_3)_2(#mu#-O)_3(#mu#_3-O)〜(6-)可能是这些簇形成的中间产物。除[{Ru(#eta#〜6-p-MeC_6H_4iPr)} _ 4Mo_4O_(16)]以外,簇结构保留在溶液中,该异构化为三-古巴仑形式。

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