Reactions of Ru₃(CO)₁₂ with ene-yne and alkoxy-silyl functionalized compounds. the crystal structure of (μ-H)Ru ₃(CO)₉[μ₃-η²-HC=N(CH ₂)₃Si(OEt)₃]

Ru₃(CO)₁₂ has been reacted with the compounds hex-1-en-3-yne [Et CCH=CH₂], 2-methyl-hex-1-en-3-yne [Et CC(=CH ₂)CH₃] and with 3(ethoxy-silyl)propyl isocyanate [(EtO)₃Si(CH₂)₃NCO] and the compound tb [(EtO)₃Si(CH₂)₃NHC(=O)OCH₂C CCH ₂OC(=O)NH(CH₂)₃Si(OEt)₃] in hydrocarbon solution. Some reactions in CH₃OH/KOH solution (followed by acidification) have also been performed. The main products of the reactions with ene-ynes are the clusters Ru₃(CO)₆(μ-CO) ₂L₂ (L = C₆H₈, C₇H ₁₀) and their demolition products, the "ferrole" Ru ₂(CO)₆L₂ complexes. One of the isomers of Ru₃(CO)₆(μ-CO)₂L₂, and Ru ₂(CO)₆L₂ (L = C₇H₁₀) have been reacted with vinyl-triethoxysilane [(EtO)₃SiCH=CH₂]: these reactions did not afford complexes containing new carbon-carbon bonds or triethoxy-silyl groups. Only polymerization of vinyl-triethoxysilane occurred. The reactions of Ru₃(CO)₁₂ with triethoxysilyl-propyl- isocyanate and tb (in the presence of Me₃NO) lead to the same products, that is the isomeric complexes (μ-H)Ru₃(CO) ₉[C=N(H)(CH₂)₃Si(OEt)₃] with a "perpendicular" ligand (complex 3, as proposed on the basis of spectroscopic results) and (μ-H)Ru₃(CO)₉[HC=N(CH ₂)₃Si(OEt)₃] with a "parallel" ligand (complex 4, as confirmed by a X-ray analysis). The reaction pathways leading to these products are discussed. Complex 4 has been reacted with tetraethyl orthosilicate and the resulting material has been characterized. These reactions are part of a study on the synthesis of inorganic-organometallic materials through sol-gel techniques.