Reactions of Ru3(CO)12 with Ene-yne and Alkoxy-silyl Functionalized Compounds. The Crystal Structure of (μ-H)Ru3(CO)9[μ3-η2-HC=N(CH2)3Si(OEt)3] |
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Authors: | Giuliana Gervasio Domenica Marabello Enrico Sappa and Andrea Secco |
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Institution: | (1) Dipartimento di Chimica IFM, Universita’ di Torino, Via Pietro Giuria 7, I-10125 Torino, Italy;(2) Dipartimento di Scienze e Tecnologie Avanzate (DiSTA), Universita’ del Piemonte Orientale, Via Bellini 25g, 15100 Alessandria, Italy |
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Abstract: | Ru3(CO)12 has been reacted with the compounds hex-1-en-3-yne EtC≡CCH=CH2], 2-methyl-hex-1-en-3-yne EtC≡CC(=CH2)CH3] and with 3(ethoxy-silyl)propyl isocyanate (EtO)3Si(CH2)3NCO] and the compound tb (EtO)3Si(CH2)3NHC(=O)OCH2C≡CCH2OC(=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, C7H10) and their demolition products, the “ferrole” Ru2(CO)6L2 complexes. One of the isomers of Ru3(CO)6(μ-CO)2L2, and Ru2(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)9C=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)9HC=N(CH2)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.
This paper is dedicated to Prof. Gunther Schmid in the occasion of his 70th birthday. |
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Keywords: | Ruthenium carbonyl Ene-yne compounds Alkoxy-silyl compounds Inorganic-organometallic materials Sol– gel |
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