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Metal complexes containing oxygen tripod ligands: Models of metal oxides

Posted on:2004-09-12Degree:Ph.DType:Dissertation
University:Hong Kong University of Science and Technology (People's Republic of China)Candidate:Lam, Chong HoFull Text:PDF
GTID:1451390011456516Subject:Chemistry
Abstract/Summary:PDF Full Text Request
Treatment of NaLOEt (Na[(η5-C5H 5)Co{lcub}P(O)(OC2H5)2{rcub}3]) with 1 equiv. of [Ti(O-i-Pr)2Cl2] and HCl in Et2O gave [LOEtTiCl3]. Reaction between [LOEtTiCl3] and tetrachlorocatechol (C6Cl 4(OH)2) gave [LOEtTi(Cl)(C6Cl 4O2)], which formed mono-μ-oxo complex [{lcub}LOEtTi(C 6Cl4O2){rcub}2(μ-O)] in the presence of base. Reaction of NaLOEt with titanyl sulfate/zirconyl nitrate and HBF4 gave [LOEtTiF3] or [LOEtZrF 3] respectively. Reaction between [LOEtTiCl3] and HOTf gave [LOEtTi(OTf)3] (OTf = triflate), which is an active catalyst for Diels-Alder reaction. [LOEtTiCl 3] can catalyze solvent-free ring opening of epoxides by Me3SiN 3.; Depending on the conc. of sulfuric acid, reaction between NaLOEt and titanyl sulfate gave [(LOEtTi)2(μ-O) 2(μ-SO4)] or [(LOEtTi)2(μ-O)(μ-SO 4)2]. Reaction of NaLOEt with titanyl sulfate in the presence of Na4P2O7, Na3PO 4 or Na2Cr2O7 gave [(LOEtTi) 2(μ-C)(μ4-P2O7)2], [LOEtTi)3(μ-O)3(μ3-PO 4)] or [(LOEtTi)2(μ-CrO4)3 ] respectively. [(LOEtTi)2(μ-CrO4) 3] can oxidize cyclohexanol to cyclohexanone. Interaction between [(L OEtTi)2(μ-O)2(μ-SO4)] and [NEt 4][Cr2O7] gave trinuclear [L OEtTi)3(μ-C)3(μ3-SO4)][HCrO 4]. Treatment of [(LOEtTi)2(μ-O)2(μ-SO 4)] with AgOTf gave [(LOEtTi)3(μ-O)2(μ 3-O)(μ3-SO4)(AgOTf)][OTf]. Zinc reduction of [(LOEtTi)2(μ-O)2(μ-SO4)] in TsOH gave a Ti(III) aqua complex [LOEtTi(OTs)2(H 2O)] (OTs = tosylate).; Interaction between zirconyl nitrate and NaLOEt followed by extraction with CH2Cl2 gave tetranuclear [(LOEt Zr)4(H2O)2(μ-OH)4(μ 3-O)2][NO3]4. Reaction of zirconyl nitrate with NaLOEt in 6.5 wt % HNO3 gave [LOEt Zr(NO3)3]. Reaction between zirconyl nitrate with two equiv. of NaLOEt gave [(LOEt)2Zr(NO 3)][NO3]. Treatment of zirconyl nitrate with NaLOEt in H2SO4 gave [(LOEt)2Zr(NO 3)][LOEtZr(NO3)(SO4)]. (Abstract shortened by UMI.)...
Keywords/Search Tags:Oet, Nal, Zirconyl nitrate, Reaction, Ticl
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