Synthesis of Rare-Earth-Metal Iminopyrrolyl Complexes from Alkyl Precursors: Ln鈫扐l N-Ancillary Ligand Transfer

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• 作者：Hiroshi Kaneko ; H. Martin Dietrich ; Christoph Sch盲dle ; C盲cilia Maichle-M枚ssmer ; Hayato Tsurugi ; Karl W. T枚rnroos ; Kazushi Mashima ; Reiner Anwander
• 刊名：Organometallics
• 出版年：2013
• 出版时间：March 11, 2013
• 年：2013
• 卷：32
• 期：5
• 页码：1199-1208
• 全文大小：477K
• 年卷期：v.32,no.5(March 11, 2013)
• ISSN：1520-6041

文摘

Protonolysis of [YMe₃]_n with 2-{(N-2,6-dialkylphenyl)iminomethyl)}pyrroles (alkyl = iPr (L¹), Me (L²)) gave homoleptic iminopyrrolyl complexes YL¹₃ and YL²₃ as well as the complex [L²YL^2,Me]₂ containing a dianionic pyrrolaldiminato ligand, formed via methylation of the imino backbone. Treatment of the half-sandwich complex [(C₅Me₅)YMe₂]₃ and yttrocene (C₅Me₅)₂YMe(THF) with either 2 or 1 equiv of HL afforded the monomeric complexes (C₅Me₅)YL₂ and (C₅Me₅)₂YL,respectively. The complex (C₅Me₅)YL²₂ readily underwent Ln鈫扐l iminopyrrolyl ligand transfer in the presence of trimethylaluminum, producing the known (C₅Me₅)Y(AlMe₄)₂. Salt metatheses of homoleptic Ln(AlMe₄)₃ (Ln = Y, La) with KL gave complicated reaction mixtures from which the 畏⁵/畏¹:魏¹ pyrrolaldiminato-bridged complex [L^1,MeLa(AlMe₄)]₂ and bis(tetramethylaluminate) complex L²Y(AlMe₄)₂ could be isolated and crystallographically characterized. Moreover, the solid-state structures of YL²₃, [L²YL^2,Me]₂, (C₅Me₅)YL¹₂, (C₅Me₅)₂YL¹, and L²AlMe₂ are presented.