Synthesis, Structure, and Reactivity of Lanthanide Complexes Incorporating Indolyl Ligands in Novel Hapticities

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• 作者：Zhijun Feng ; Xiancui Zhu ; Shaoyin Wang ; Shaowu Wang ; Shuangliu Zhou ; Yun Wei ; Guangchao Zhang ; Baojia Deng ; Xiaolong Mu
• 刊名：Inorganic Chemistry
• 出版年：2013
• 出版时间：August 19, 2013
• 年：2013
• 卷：52
• 期：16
• 页码：9549-9556
• 全文大小：481K
• 年卷期：v.52,no.16(August 19, 2013)
• ISSN：1520-510X

文摘

The chemistry of interactions of 2-(2,6-diisopropylphenylaminomethylene)indole ligand (1) with europium and ytterbium amides is described. Reaction of 2-(2,6-diisopropylphenylaminomethylene)indole 2-(2,6-i-Pr₂C₆H₃NHCH₂)C₈H₅NH (1) with europium amide [(Me₃Si)₂N]₃Eu^III(渭-Cl)Li(THF)₃ afforded a novel europium(II) complex formulated as {[渭-畏⁶:畏¹:畏¹-2-(2,6-i-Pr₂C₆H₃N鈺怌H)C₈H₅N]Eu[2-(2,6-i-Pr₂C₆H₃N鈺怌H)C₈H₅N]}₂ (2), having a bridged indolyl ligand in the novel 渭-畏⁶:畏¹:畏¹ hapticities with the reduction of europium(III) to europium(II) and the oxidation of amino to imino group. Reaction of 2-(2,6-diisopropylphenylaminomethylene)indole 2-(2,6-i-Pr₂C₆H₃NHCH₂)C₈H₅NH (1) with ytterbium(III) amide [(Me₃Si)₂N]₃Yb^III(渭-Cl)Li(THF)₃ produced the only deprotonated ytterbium(III) complex formulated as [2-(2,6-i-Pr₂C₆H₃NCH₂)C₈H₅N]Yb[N(SiMe₃)₂](THF)₂ (3), having an 畏¹ hapticity indolyl ligand. Reaction of 2 with formamidine [(2,6-Me₂C₆H₃)NCHNH(C₆H₃Me₂-2,6)] produced {[渭-畏³:畏¹:畏¹-2-(2,6-i-Pr₂C₆H₃N鈺怌H)C₈H₅N]Eu[(2,6-Me₂C₆H₃)NCHN(C₆H₃Me₂-2,6)](THF)}₂ (4), which has a bridged indolyl ligand in the novel 渭-畏³:畏¹:畏¹ hapticities, whereas the reaction of 2 with the more sterically bulky formamidine [(2,6-i-Pr₂C₆H₃)NCHNH(C₆H₃i-Pr₂-2,6)] afforded complex {[渭-畏²:畏¹:畏¹-2-(2,6-i-Pr₂C₆H₃N鈺怌H)C₈H₅N]Eu[(2,6-i-Pr₂C₆H₃)N鈺怌HN(C₆H₃i-Pr₂-2,6)](THF)}₂ (5), having the indolyl ligand in the novel 渭-畏²:畏¹:畏¹ hapticities. The results represent the first example of organometallic complexes having indolyl ligands in the novel 渭-畏⁶:畏¹:畏¹, 渭-畏³:畏¹:畏¹, and 渭-畏²:畏¹:畏¹ bonding modes with metal.