Synthesis and Properties of Ferrocenyl Allenylidene Complexes: X-ray Structure of [Ru(C═C═CHFc)(PPh3)2(η5-C5H5)][PF6]

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• 作者：Lindsay T. Byrne ; George A. Koutsantonis ; Vanessa Sanford ; John P. Selegue ; Phil A. Schauer ; Ramnath S. Iyer
• 刊名：Organometallics
• 出版年：2010
• 出版时间：March 8, 2010
• 年：2010
• 卷：29
• 期：5
• 页码：1199-1209
• 全文大小：975K
• 年卷期：v.29,no.5(March 8, 2010)
• ISSN：1520-6041

文摘

Reactions of the transition metal halide complexes [MXL₂(Cp)] (M = Fe, X = I, L₂ = dppe; M = Ru, X = Cl, L = PPh₃; M = Os, X = Br, L = PPh₃; Cp = η-C₅H₅) with the alkynol HC≡CCH(OH)(Fc) (1) (Fc = ferrocenyl) in the presence of TlBF₄ gave the monosubstituted allenylidene complexes [M(C═C═CHFc)L₂(Cp)][BF₄] (2a: M = Ru, L = PPh₃; 3: M = Fe, L₂ = dppe; 4: M = Os, L = PPh₃). Similarly, the reaction of 1 with [RuCl(PPh₃)₂(Cp)] and NH₄PF₆ in methanol gave [Ru(C═C═CHFc)(PPh₃)₂(Cp)][PF₆] (2b). These highly colored compounds were characterized by spectroscopic and electrochemical techniques and in the case of 2b by a single-crystal X-ray structure determination. Cyclic voltammetry in MeCN in the presence of [p>np>Bu₄N][ClO₄] at 100 mV·sp>−1p> shows a reversible ferrocenyl-based one-electron oxidation, in addition to irreversible oxidation and reduction processes. The NMR spectra of 2b show complex behavior at low temperature, attributed to temperature-dependent chemical shifts and correlated motions of the allenylidene ligand and the ferrocenyl substituent.