Yb(II) Triple-Decker Complex with the μ-Bridging Naphthalene Dianion [CpBn5Yb(DME)]2(μ-η4:η4-C10H8). Oxidative Substitution of [C10H8]2– by 1,4-Diphenylbuta-1,3-diene and P4 and Protonolysis of the Yb–C10H8 Bond by PhPH2

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• 作者：Alexander N. Selikhov ; Tatyana V. Mahrova ; Anton V. Cherkasov ; Georgy K. Fukin ; Evgueni Kirillov ; Carlos Alvarez Lamsfus ; Laurent Maron ; Alexander A. Trifonov
• 刊名：Organometallics
• 出版年：2016
• 出版时间：July 25, 2016
• 年：2016
• 卷：35
• 期：14
• 页码：2401-2409
• 全文大小：525K
• 年卷期：0
• ISSN：1520-6041

文摘

Two synthetic approaches to the new three-decker Yb(II) complex [Cp^Bn5Yb(DME)]₂[μ-C₁₀H₈] (1) were successfully employed: the reaction of [Cp^Bn5Yb(DME)(μ-I)]₂ (2) with 2 molar equiv of [C₁₀H₈]⁻·K in DME and the reaction of [YbI(DME)₂]₂[μ-C₁₀H₈] (3) with Cp^Bn5K in a 1:2 molar ratio in DME. Complex 1 was proved to be a Yb(II) binuclear triple-decker complex containing a dianionic naphthalene ligand bridging two Cp^Bn5Yb(DME) fragments in a μ-η⁴:η⁴ fashion. An oxidative substitution of (C₁₀H₈)^2– by trans-(1E,3E)-1,4-diphenylbuta-1,3-diene afforded the three-decker Yb(II) complex [Cp^Bn5Yb(DME)]₂(μ-η⁴:η⁴ -PhCHCHCHCHPh) (4) with a dianionic μ-η⁴:η⁴-bridging diphenylbutadiene ligand and naphthalene. The reaction of 1 with excess P₄ also occurs with oxidation of (C₁₀H₈)^2–, whereas Yb remains divalent. The reaction results in the formation of the trinuclear Yb(II) complex with a μ-bridging P₇^3– ligand [Cp^Bn5Yb(DME)]₃(P₇) (5). Protonation of the Yb–C₁₀H₈ bond in 1 with PhPH₂ (1:2 molar ratio) afforded the dimeric phosphido complex [Cp^Bn5Yb(THF)(μ₂-PHPh)]₂ (6) in 64% yield, while an attempt to obtain a phosphinidene Yb(II) species by reacting equimolar amounts of 1 and PhPH₂ in DME resulted in the isolation of the metallocene complex Cp^Bn5₂Yb(DME) (7).