Synthesis and Structures of Titanosiloxane Cage Compounds |
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Authors: | Jeong Hyun Kim Seung-Hyun Kang Il Nam Jung Kwan Mook Kim Bok Ryul Yoo Myong Euy Lee |
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Institution: | (1) Organosilicon Chemistry Laboratory, Korea Institute of Science and Technology, P.O. Box 131, Cheongryang, Seoul, 130-650, Korea;(2) Department of Chemistry, Graduate School, Yonsei University, Seoul, 120-749, Korea |
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Abstract: | Reaction of (triphenylmethyl)silanetriol (1) with cyclopentadienyltitanium trichloride (CpTiCl3) in the presence of triethylamine as a HCl scavenger gave both compounds of a partial open-cage type {Ph3CSiO(OH)]3(Ph3CSiO3/2)(CpTiO3/2)4} (2) and cube type (Ph3CSiO3/2CpTiO3/2)4 (3). The 1:1 reaction of 1 and CpTiCl3 in toluene solvent at reflux temperature for 3 d afforded compounds 2 (22%) and 3 (36%). When 1 is reacted with a 1.5 fold excess of CpTiCl3 under the same conditions, compound 3 was obtained in high yield (81%) along with 2 in trace quantities. Compounds 2 and 3 were fully characterized by the analyses of 1H, 13C, 29Si NMR, IR, and FAB MS data. The solid-state structure of 3 was determined by a single crystal X-ray diffraction study. Compound 3 had shown to have catalytic activity for the oxidation of alkenes such as 1-octene, cyclooctene, and norbornene with t-butyl hydrogen peroxide. The effect of solvent was observed in this epoxidation reaction. The order of reactivity were decreased as follows: CHCl3 > hexane THF. |
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Keywords: | slanetriol cage compounds polytitanosiloxane polytitanosilsesquioxane cyclopentadienyltitanium trichloride alkene |
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