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Reactions of Co2(CO)8 and of Co2(CO)6L (L = 3-pentyn-1-ol, 1,4-butyn-diol or 2-methyl-3-butyn-2-ol) with 2(diphenylphosphino)ethyl-trietoxysilane and tris(hydroxymethyl)phosphine for applications to new sol-gel materials
Authors:Fabio Carniato  Giuliana Gervasio  Enrico Sappa  Andrea Secco
Institution:a Dipartimento di Scienze e Tecnologie Avanzate, Centro Interdisciplinare Nano-Sistemi, Università del Piemonte Orientale, Via Teresa Michel 11, I-15100 Alessandria, Italy
b Dipartimento di Chimica IFM, Università di Torino, Centro Interdipartimentale di Cristallografia Diffrattometrica CrisDi, via Pietro Giuria 7, I-10125 Torino, Italy
Abstract:The complex Co2(CO)6μ-η2-(H3CCtriple bond; length of mdashCCH2CH2OH)] (1) with the ligand 3-pentyn-1-ol (pol) has been synthesized following established procedures. Its structure has been determined by X-ray analysis. The complex Co2(CO)6(mbo) (mbo = 2-methyl-3-butyn-2-ol, HCtriple bond; length of mdashCC(CH3)2OH), (3), along with the already known Co2(CO)6(bud) (bud = 1,4-butyn-diol, HOCH2Ctriple bond; length of mdashCCH2OH) (2), and Co2(CO)8 were reacted with 2(diphenylphosphino)ethyl-triethoxysilane Ph2PCH2CH2Si(OCH2CH3)3] (dpts) and tris(hydroxymethyl)phosphine P(CH2OH)3] (thp). With dpts, mono- and di-substituted complexes were obtained: these were characterized by analytical and spectroscopic techniques. The structures of Co2(CO)6(dpts)2 (5) and of Co2(CO)4(pol)(dpts)2 (8) have been determined by X-ray analysis.Complex (1) was reacted with 3-(triethoxysilyl)propyl isocyanate (H3CCH2O)3Si(CH2)3NCO] (tsi): the new complex Co2(CO)6H3CCtriple bond; length of mdashCCH2CH2OC(double bond; length as m-dashO)NH(CH2)3Si(OCH2CH3)3] (9) was obtained and spectroscopically characterized. The complex has also been reacted with tetraethyl orthosilicate (teos); a new inorganic-organometallic material was obtained. Complex (5) has been grafted on the mesoporous material SBA-15. The hybrid inorganic-organometallic materials obtained have been characterized by inductively coupled plasma-mass spectrometry (ICP-MS), infrared spectroscopy (FT-IR) under vacuum conditions, X-ray diffraction (XRD) and scanning electron microscopy coupled to EDS probe (SEM-EDS).
Keywords:Cobalt carbonyls  Functionalized alkynes  Triethoxysilyl ligands  Sol-gel inorganic-organometallic materials  Molecular structure
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