Synthesis, characterisation and reactivity of siloxyl-substituted derivatives of [Ru3(CO)12]. Crystal structure of trans-[Ru2(CO)8{Si(OSiMe3)3}2]
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Abstract
Thermal reactions of the bulky siloxysilanes HSi(OSiMe3)3 and HSiMe(OSiMe3)2 with [Ru3(CO)12] led to the formation of siloxyl-substituted triruthenium clusters. Formal replacement of one or more CO ligands from [Ru3(CO)12] via oxidative addition generates [Ru3H(CO)11{η1-Si(OSiMe3)3}] 1, [Ru3H2(CO)10{η1-Si(OSiMe3)3}2] 3, [Ru3H(CO)11{η1-SiMe(OSiMe3)2}] 4 and [Ru3H2(CO)10{η1-SiMe(OSiMe3)2}2] 6. Also formed are [Ru3H(CO)10{η2-Si(OSiMe3)3}] 2 and [Ru3H(CO)10{η2-SiMe(OSiMe3)2}] 5 in which a second CO molecule has been displaced from clusters 1 and 4 respectively, resulting in the formation of a dative SiO→Ru interaction. The siloxyl-substituted compounds are thermodynamically unstable and decompose to dinuclear species, [Ru2(CO)8{Si(OR)3}2], and [Ru4H4(CO)12] within several hours. Alternatively the dinuclear complexes can be synthesized cleanly and selectively by the photochemical reaction of [Ru3(CO)12] with the appropriate silane and trans-[Ru2(CO)8{Si(OSiMe3)3}2] 7 has been characterised by X-ray crystallography at 193 K. The structure is strongly disordered.
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