Synthetic Aspects of (C5H4SiMe3)3Ln Rare-Earth Chemistry: Formation of (C5H4SiMe3)3Lu via [(C5H4

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• 作者：Jeffrey K. Peterson ; Matthew R. MacDonald ; Joseph W. Ziller ; William J. Evans
• 刊名：Organometallics
• 出版年：2013
• 出版时间：May 13, 2013
• 年：2013
• 卷：32
• 期：9
• 页码：2625-2631
• 全文大小：444K
• 年卷期：v.32,no.9(May 13, 2013)
• ISSN：1520-6041

文摘

New analogues of Cp鈥?sub>3b>Ln (Cp鈥?= Cb>5b>Hb>4b>SiMeb>3b>, Ln = rare earth) complexes have been synthesized with the largest and smallest lanthanides, La and Lu. Due to the smaller size of Lu, the reaction of LuClb>3b> with 3 equiv of KCp鈥?produced only traces of Cp鈥?sub>3b>Lu, yielding [Cp鈥?sub>2b>Lu(渭-Cl)]b>2b> as the major product. An alternative route was developed in which [Cp鈥?sub>2b>Lu(渭-Cl)]b>2b> reacts with (Cb>3b>Hb>5b>)MgCl to form the tetrameric allyl complex [Cp鈥?sub>2b>Lu(渭-畏¹:畏¹-Cb>3b>Hb>5b>)]b>4b>. The allyl complex reacts with [HNEtb>3b>][BPhb>4b>] to generate [Cp鈥?sub>2b>Lu(THF)b>2b>][BPhb>4b>], which reacts with KCp鈥?to produce Cp鈥?sub>3b>Lu in good yield. The reaction of LaClb>3b> with 3 equiv of KCp鈥?in Etb>2b>O gave the unsolvated Cp鈥?sub>3b>La, while the same reaction in rigorously dry THF gave solvated Cp鈥?sub>3b>La(THF). The reaction of LaClb>3b> and KCp鈥?in improperly dried THF gave the mixed-ligand complex Cp鈥?sub>2b>CpLa(THF) (Cp = Cb>5b>Hb>5b>), rather than the expected hydrolysis product, [Cp鈥?sub>2b>La(渭-OH)]b>2b>.