Metal complexes containing oxygen tripod ligands: Models of metal oxides.

摘要

Treatment of NaL_OEt (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 [L_OEtTiCl₃]. Reaction between [L_OEtTiCl₃] and tetrachlorocatechol (C₆Cl ₄(OH)₂) gave [L_OEtTi(Cl)(C₆Cl ₄O₂)], which formed mono-μ-oxo complex [{lcub}L_OEtTi(C ₆Cl₄O₂){rcub}₂(μ-O)] in the presence of base. Reaction of NaL_OEt with titanyl sulfate/zirconyl nitrate and HBF₄ gave [L_OEtTiF₃] or [L_OEtZrF ₃] respectively. Reaction between [L_OEtTiCl₃] and HOTf gave [L_OEtTi(OTf)₃] (OTf = triflate), which is an active catalyst for Diels-Alder reaction. [L_OEtTiCl ₃] can catalyze solvent-free ring opening of epoxides by Me₃SiN ₃.; Depending on the conc. of sulfuric acid, reaction between NaL_OEt and titanyl sulfate gave [(L_OEtTi)₂(μ-O) ₂(μ-SO₄)] or [(L_OEtTi)₂(μ-O)(μ-SO ₄)₂]. Reaction of NaL_OEt with titanyl sulfate in the presence of Na₄P₂O₇, Na₃PO ₄ or Na₂Cr₂O₇ gave [(L_OEtTi) ₂(μ-C)(μ₄-P₂O₇)₂], [L_OEtTi)₃(μ-O)₃(μ₃-PO ₄)] or [(L_OEtTi)₂(μ-CrO₄)₃ ] respectively. [(L_OEtTi)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 [(L_OEtTi)₂(μ-O)₂(μ-SO ₄)] with AgOTf gave [(L_OEtTi)₃(μ-O)₂(μ ₃-O)(μ₃-SO₄)(AgOTf)][OTf]. Zinc reduction of [(L_OEtTi)₂(μ-O)₂(μ-SO₄)] in TsOH gave a Ti(III) aqua complex [L_OEtTi(OTs)₂(H ₂O)] (OTs = tosylate).; Interaction between zirconyl nitrate and NaL_OEt followed by extraction with CH₂Cl₂ gave tetranuclear [(L_OEt Zr)₄(H₂O)₂(μ-OH)₄(μ ₃-O)₂][NO₃]₄. Reaction of zirconyl nitrate with NaL_OEt in 6.5 wt % HNO₃ gave [L_OEt Zr(NO₃)₃]. Reaction between zirconyl nitrate with two equiv. of NaL_OEt gave [(L_OEt)₂Zr(NO ₃)][NO₃]. Treatment of zirconyl nitrate with NaL_OEt in H₂SO₄ gave [(L_OEt)₂Zr(NO ₃)][L_OEtZr(NO₃)(SO₄)]. (Abstract shortened by UMI.)