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• 作者：Jutzi ; Peter ; Redeker ; Thomas ; Neumann ; Beate ; Stammler ; Hans-Georg
• 关键词：Titanium ; Zirconium ; Half-sandwich ; (Diisopropylaminoethyl)cyclopentadienyl ligand
• 刊名：Journal of Organometallic Chemistry
• 出版年：1997
• 出版时间：April 15, 1997
• 年：1997
• 卷：533
• 期：1-2
• 页码：237-245
• 全文大小：921 K

文摘

The synthesis of titanium and zirconium complexes with the donor functionalized 2-(N,N-diisopropylaminoethyl)cyclopentadienyl (Cp^N) ligand is described. The reaction of TiCl₄ with (C₅H₄CH₂CH₂NⁱPr₂)Li leads to the formation of the highly moisture-sensitive half-sandwich complex (C₅H₄CH₂CH₂NⁱPr₂)TiCl₃ (1), which easily forms a coordination polymer. Complex 1 reacts with one equivalent of HCl under protonation of the amino group to give the monomeric hydrochloride [(C₅H₄CH₂CH₂N(H)ⁱPr₂)TiCl₃]⁺Cl⁻ (2), which shows excellent solubility in polar solvents. The compound (C₅H₄CH₂CH₂NⁱPr₂)Ti(NMe₂)₃ (3) is prepared by the reaction of Ti(NMe₂)₄ with one equivalent of C₅H₅CH₂CH₂NⁱPr₂ (Cp^NH). Reaction of 3 with three equivalents of isopropanol affords the isopropoxy derivative (C₅H₄CH₂CH₂NⁱPr₂)Ti(OⁱPr)₃ (4) in quantitative yield. The reaction of (C₅H₄CH₂C₂NⁱPr₂)Li with Me₃SiCl leads to the formation of the Cp^N-transfer reagent (C₅H₄CH₂CH₂NⁱPr₂)SiMe₃ (5). The polymeric zirconium compound [(C₅H₄CH₂CH₂NⁱPr₂)ZrCl₃]_x (6) is synthesized by the reaction of 5 with ZrCl₄. 6 reacts with one equivalent of HCl under protonation of the amino group to give the monomeric air- and moisture-stable hydrochloride [(C₅H₄CH₂CH₂N(H)ⁱPr₂)ZrCl₃]⁺Cl⁻ · 2CH₃OH (7). The structure of 7 has been determined by single-crystal X-ray diffractometry. The reaction of 7 with water leads under exchange of the donor ligands to the formation of the air- and water-stable hydrochloride [(C₅H₄CH₂CH₂N(H)ⁱPr₂)ZrCl₃]⁺Cl⁻ · 2H₂O (8). The compound (C₅H₄CH₂CH₂NⁱPr₂)Zr(NMe₂)₃ (9) is prepared by the reaction of Zr(NMe₂)₄ with one equivalent of C₅H₅CH₂CH₂NⁱPr₂ is nearly quantitative yield.