Syntheses and Structures of the Crystalline, Highly Crowded 1,3-Bis(trimethylsilyl)cyclopentadienyls [MCp鈥?sub>3] (M = Y, Er, Yb), [PbCp鈥?sub>2], [{YCp鈥?sub>2(渭-OH)}2], [(

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• 作者：Martyn P. Coles ; Peter B. Hitchcock ; Michael F. Lappert ; Andrey V. Protchenko
• 刊名：Organometallics
• 出版年：2012
• 出版时间：April 9, 2012
• 年：2012
• 卷：31
• 期：7
• 页码：2682-2690
• 全文大小：507K
• 年卷期：v.31,no.7(April 9, 2012)
• ISSN：1520-6041

文摘

Yttrium and the smaller group 3 and 4f metal homoleptic M(III) cyclopentadienyls [MCp鈥?sub>3] (Cp鈥?= [畏⁵-C₅H₃(SiMe₃)₂-1,3]^{鈭?/sup> and M = Y (1Y), Er (1Er), or Yb (1Yb)) were prepared from YCp鈥?sub>2I (2Y) or the appropriate [LnCp鈥?sub>2I(thf)] and KCp鈥?in satisfactory (1Y), very low (1Er), or low (1Yb) yield. Attempted reaction of [ScCp鈥?sub>2I(thf)] with KCp鈥?failed to produce the homoleptic Sc(III) cyclopentadienyl. Compound 1Yb was synthesized in better yield by the redox reaction between [YbCp鈥?sub>2(thf)] and either [PbCp鈥?sub>2] (3) or the in situ prepared HgCp鈥?sub>2 (4) analogue. Complexes 3 and 4 were obtained by a salt metathesis route, 3 was isolated as a crystalline solid, while 4 was used only as a hexane solution. The structures of crystalline 1Y, 1Yb, 3, [{YCp鈥?sub>2(渭-OH)}₂] (5Y) [prepared by hydrolysis of 1Y], [(ScCp鈥?sub>2)₂(渭-畏2:畏2-C₂H₄)] (6) {isolated in low yield from the reaction of ScCp鈥?sub>2I (2Sc) with [K(18-crown-6)]₂[C₆H₂(SiMe₃)₄-1,2,4,5]}, [LaCp鈥?sub>2Cl(渭-Cl)K(18-crown-6)] (7La) {obtained from the foregoing potassium reagent and [{LaCp鈥?sub>2(渭-Cl)}₂]}, [YbCp鈥?sub>2Cl(渭-Cl)K(18-crown-6)] (7Yb), and [{KCp鈥硙_{鈭?/sub>] (8) were determined by X-ray diffraction.}}