Lanthanide (Sm, Dy) Complexes with the 9,10-Phenanthrenediimine Redox-Active Ligand: Synthesis and Structures

IF 1.1 3区 化学 Q4 CHEMISTRY, INORGANIC & NUCLEAR
D. K. Sinitsa, D. P. Akimkina, T. S. Sukhikh, S. N. Konchenko, N. A. Pushkarevsky
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引用次数: 0

Abstract

The complex formation of the redox-active ligand bis(N,N'-2,6-diisopropylphenyl)-9,10-phenanthrenediimine (DippPDI) with alkaline metal (Li, K) and lanthanide (Sm, Dy) cations is studied. The reduction of DippPDI with an alkaline metal excess affords the dianionic form of the ligand (DippPDA2–), which crystallizes with the potassium cation as the coordination polymer [K2(DippPDA)(Thf)3] (Thf is tetrahydrofuran). The reaction of equimolar amounts of the lithium salt with the dianionic form of the ligand and neutral diimine affords the lithium complex with the radical-anion form (DippPSI•–) crystallized as [Li(DippPSI)(Thf)2]. The samarium(III) complex [SmCp*(DippPDA)(Тhf)] (I) is formed by the reduction of DippPDI with samarocene [Sm\({\text{Cp}}_{2}^{*}\)(Thf)2] (Cp* is pentamethylcyclopentadienide): both the samarium(II) cation and Cp* anion are oxidized in the reaction. DippPDI does not react with similar ytterbocene. The dysprosium(III) complexes are synthesized by the ion exchange reactions between DyI3(Thf)3.5 and potassium or lithium salt with the DippPDA2– dianion. Similar complexes [Dy(DippPDA)I(Thf)2] (IIThf) and [Dy(DippPDA)I(Thf)(Et2O)] (\({\mathbf{I}}{{{\mathbf{I}}}^{{{\text{E}}{{{\text{t}}}_{{\text{2}}}}{\text{O}}}}}\)) are formed in the reactions with the potassium salt depending on the solvent used: a THF–hexane or a diethyl ether–n-hexane mixture, respectively. The coordination of the dysprosium cation by the π system of the conjugated fragment of the NCCN ligand is observed in IIThf, whereas in \({\mathbf{I}}{{{\mathbf{I}}}^{{{\text{E}}{{{\text{t}}}_{{\text{2}}}}{\text{O}}}}}\) this coordination is absent. The reaction with Li2(DippPDA) affords the binary complex salt [Li(Тhf)3(Et2O)][DyI2(DippPDA)(Тhf)] (III, crystallization from a THF–Et2O mixture). The crystallization from THF gives the [Li(Тhf)4][DyI2(DippPDA)(Thf)] salt (III') containing the same anion as III. The structures of all new complexes are studied by X-ray diffraction (XRD, CIF files CCDC nos. 2260307–2260313).

Abstract Image

Abstract Image

具有 9,10-菲二亚胺氧化还原活性配体的镧系元素(Sm, Dy)配合物:合成与结构
摘要 研究了氧化还原活性配体双(N,N'-2,6-二异丙基苯基)-9,10-菲二亚胺(DippPDI)与碱金属(Li、K)和镧系元素(Sm、Dy)阳离子形成的络合物。碱金属过量还原 DippPDI 会生成配体的二离子形式(DippPDA2-),该配体与钾阳离子结晶为配位聚合物 [K2(DippPDA)(Thf)3](Thf 为四氢呋喃)。等摩尔量的锂盐与配体的二阴离子形式和中性二亚胺反应后,得到了以自由基阴离子形式(DippPSI--)存在的锂配合物,其结晶为[Li(DippPSI)(Thf)2]。钐(III)络合物[SmCp*(DippPDA)(Тhf)](I)是由 DippPDI 与二茂钐[Sm\({text{Cp}}_{2}^{*}\)(Thf)2](Cp* 为五甲基环戊二烯)还原形成的:钐(II)阳离子和 Cp*- 阴离子在反应中均被氧化。DippPDI 不会与类似的镱发生反应。镝(III)配合物是通过 DyI3(Thf)3.5 和钾盐或锂盐与 DippPDA2- 二元离子的离子交换反应合成的。根据所用溶剂的不同,在与钾盐的反应中会形成类似的[Dy(DippPDA)I(Thf)2](IIThf)和[Dy(DippPDA)I(Thf)(Et2O)]({\({mathbf{I}}{{\mathbf{I}}^{{\text{E}}{{\text{t}}}_{{\text{2}}}}{\text{O}}}}})络合物:在与钾盐的反应中分别形成四氢呋喃-正己烷或二乙醚-正己烷混合物。在 IIThf 中观察到镝阳离子与 NCCN 配体共轭片段的 π 系统配位,而在({\mathbf{I}}{{\mathbf{I}}^{{\text{E}}}{{\text{t}}}_{{\text{2}}}}{\text{O}}}}}/)中则没有这种配位。与 Li2(DippPDA)反应得到二元复盐[Li(Тhf)3(Et2O)][DyI2(DippPDA)(Тhf)](III,从 THF-Et2O 混合物中结晶)。从 THF 结晶得到的[Li(Тhf)4][DyI2(DippPDA)(Thf)]盐(III')含有与 III 相同的阴离子。所有新络合物的结构均通过 X 射线衍射(XRD,CIF 文件 CCDC 编号:2260307-2260313)进行了研究。
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来源期刊
Russian Journal of Coordination Chemistry
Russian Journal of Coordination Chemistry 化学-无机化学与核化学
CiteScore
2.40
自引率
15.80%
发文量
85
审稿时长
7.2 months
期刊介绍: Russian Journal of Coordination Chemistry is a journal that publishes reviews, original papers, and short communications on all aspects of theoretical and experimental coordination chemistry. Modern coordination chemistry is an interdisciplinary science that makes a bridge between inorganic, organic, physical, analytical, and biological chemistry.
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