Reactivity of Lanthanocene Hydroxides toward Ketene, Isocyanate, Lanthanocene Alkyl, and Triscyclopentadienyllanthanide Complexes
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- 作者：Chunmei Zhang ; Ruiting Liu ; Jie Zhang ; Zhenxia Chen ; and Xigeng Zhou
- 刊名：Inorganic Chemistry
- 出版年：2006
- 出版时间：July 24, 2006
- 年：2006
- 卷：45
- 期：15
- 页码：5867 - 5877
- 全文大小：484K
- 年卷期：v.45,no.15(July 24, 2006)
- ISSN：1520-510X
文摘
The reactivity of [Cp2Ln(
-OH)(THF)]2 (Ln = Y (1), Er (2), Yb (3)) toward PhEtCCO, PhNCO, Cp3Ln, [Cp2Ln(-CH3)]2, and the LiCl adduct of Cp2LnnBu(THF)x was examined. In all cases, OH-centered reactivity is observed:complexes 1-3 react with PhEtCCO to form the O-H addition products [Cp2Ln(-
1:2-O2CCHEtPh)]2 (Ln = Yb(5), Er (6), Y (7), respectively, for 1-3), whereas treatment of 1 with PhNCO affords the addition/CpH-elimination/rearrangement product [{Cp2Y(THF)}2(-2:2-O2CNPh)] (8), which contains an unusual PhNCO2 dianionic ligand.Analogous compound [Cp2Ln(THF)]2(-2:2-O2CNPh) (Ln = Yb (9), Er (10)) and 8 can be obtained in a higheryield by treatment of [Cp2Ln(-OH)(THF)]2 with PhNCO followed by reaction with the corresponding Cp3Ln. However,attempts to prepare the corresponding heterobimetallic complex by reacting stoichiometric amounts of [Cp2Y(-OH)(THF)]2 with PhNCO followed by treating it with Cp3Yb are unsuccessful. Instead, only rearrangement products8 and 9 are obtained. Furthermore, the reaction of 3 with [Cp2Yb(-CH3)]2 or Cp3Yb forms oxo-bridged compound[Cp2Yb(THF)]2(-O) (11), whereas the reaction of [Cp2ErCl]2 with LinBu followed by treatment with 2 affords unexpected-oxo lanthanocene cluster (Cp2Er)3(-OH)(3-O)(-Cl)Li(THF)4 (12). In contrast to 1 and 2, 3 shows a strongtendency to undergo the intermolecular elimination of CpH at room temperature, giving trinuclear species [Cp2Yb(-OH)]2[CpYb(THF)](3-O) (4). The single-crystal X-ray diffraction structures of 1, 2, and 4-12 are described.All the results offer an interesting contrast to transition- and main-metal hydroxide complexes.
-OH)(THF)]2 (Ln = Y (1), Er (2), Yb (3)) toward PhEtCCO, PhNCO, Cp3Ln, [Cp2Ln(-CH3)]2, and the LiCl adduct of Cp2LnnBu(THF)x was examined. In all cases, OH-centered reactivity is observed:complexes 1-3 react with PhEtCCO to form the O-H addition products [Cp2Ln(-1:2-O2CCHEtPh)]2 (Ln = Yb(5), Er (6), Y (7), respectively, for 1-3), whereas treatment of 1 with PhNCO affords the addition/CpH-elimination/rearrangement product [{Cp2Y(THF)}2(-2:2-O2CNPh)] (8), which contains an unusual PhNCO2 dianionic ligand.Analogous compound [Cp2Ln(THF)]2(-2:2-O2CNPh) (Ln = Yb (9), Er (10)) and 8 can be obtained in a higheryield by treatment of [Cp2Ln(-OH)(THF)]2 with PhNCO followed by reaction with the corresponding Cp3Ln. However,attempts to prepare the corresponding heterobimetallic complex by reacting stoichiometric amounts of [Cp2Y(-OH)(THF)]2 with PhNCO followed by treating it with Cp3Yb are unsuccessful. Instead, only rearrangement products8 and 9 are obtained. Furthermore, the reaction of 3 with [Cp2Yb(-CH3)]2 or Cp3Yb forms oxo-bridged compound[Cp2Yb(THF)]2(-O) (11), whereas the reaction of [Cp2ErCl]2 with LinBu followed by treatment with 2 affords unexpected-oxo lanthanocene cluster (Cp2Er)3(-OH)(3-O)(-Cl)Li(THF)4 (12). In contrast to 1 and 2, 3 shows a strongtendency to undergo the intermolecular elimination of CpH at room temperature, giving trinuclear species [Cp2Yb(-OH)]2[CpYb(THF)](3-O) (4). The single-crystal X-ray diffraction structures of 1, 2, and 4-12 are described.All the results offer an interesting contrast to transition- and main-metal hydroxide complexes.