Synthesis and Structure of Silicon-Bridged Boratabenzene Fluorenyl Rare-Earth Metal Complexes

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• 作者：Chunhong Wang ; Li Xiang ; Xuebing Leng ; Yaofeng Chen
• 刊名：Organometallics
• 出版年：2016
• 出版时间：June 13, 2016
• 年：2016
• 卷：35
• 期：11
• 页码：1995-2002
• 全文大小：535K
• 年卷期：0
• ISSN：1520-6041

文摘

A silicon-bridged boratabenzene fluorenyl ligand [Me₂Si(C₁₃H₈)(C₅H₄BNEt₂)]^2– (L^2–) was designed and synthesized. By employment of this ligand, two divalent rare-earth metal complexes [Me₂Si(C₁₃H₈)(C₅H₄BNEt₂)]Ln(THF)₂ (Ln = Sm (1), Yb (2)) were obtained from salt metathesis of K₂[Me₂Si(C₁₃H₈)(C₅H₄BNEt₂)] (K₂L) with LnI₂(THF)₂ in THF. Complex 2 undergoes redox reaction with cyclooctatetraene to give a trivalent Yb complex [(C₈H₈)Yb]₂[μ-{Me₂Si(C₁₃H₈)(C₅H₄BNEt₂)}₂] (3), accompanied with oxidative coupling of two fluorenyl groups. A series of chloro-bridged trimeric trivalent rare-earth metal complexes [Li(THF)₄]₂[{[Me₂Si(C₁₃H₈)(C₅H₄BNEt₂)]Ln(μ-Cl)Li(THF)₃}₃(μ-Cl)₃(μ₃-Cl)₂] (Ln = Nd (4), Sm (5), and Gd (6)) were synthesized by reactions of Li₂[Me₂Si(C₁₃H₈)(C₅H₄BNEt₂)] (Li₂L) with LnCl₃ in THF. Treatment of K₂[Me₂Si(C₁₃H₈)(C₅H₄BNEt₂)] (K₂L) with LnI₃(THF)_n gave the monomeric complexes [Me₂Si(C₁₃H₈)(C₅H₄BNEt₂)]LnI(THF) (Ln = La (7), Nd (8), Sm (9), and Gd (10)). These iodides were subsequently reacted with K[CH₂C₆H₄-o-NMe₂] to afford THF coordinated benzyl complexes [Me₂Si(C₁₃H₈)(C₅H₄BNEt₂)]Ln(CH₂C₆H₄-o-NMe₂)(THF) (Ln = La (11), Nd (12), and Gd (13a)) and non-THF coordinated complex [Me₂Si(C₁₃H₈)(C₅H₄BNEt₂)]Gd(CH₂C₆H₄-o-NMe₂) (13b).