D. K. Sinitsa, D. P. Akimkina, T. S. Sukhikh, S. N. Konchenko, N. A. Pushkarevsky
{"title":"Lanthanide (Sm, Dy) Complexes with the 9,10-Phenanthrenediimine Redox-Active Ligand: Synthesis and Structures","authors":"D. K. Sinitsa, D. P. Akimkina, T. S. Sukhikh, S. N. Konchenko, N. A. Pushkarevsky","doi":"10.1134/S1070328423601012","DOIUrl":null,"url":null,"abstract":"<p>The complex formation of the redox-active ligand bis(<i>N</i>,<i>N</i>'-2,6-diisopropylphenyl)-9,10-phenanthrenediimine (<sup>Dipp</sup>PDI) with alkaline metal (Li, K) and lanthanide (Sm, Dy) cations is studied. The reduction of <sup>Dipp</sup>PDI with an alkaline metal excess affords the dianionic form of the ligand (<sup>Dipp</sup>PDA<sup>2–</sup>), which crystallizes with the potassium cation as the coordination polymer [K<sub>2</sub>(<sup>Dipp</sup>PDA)(Thf)<sub>3</sub>] (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 (<sup>Dipp</sup>PSI<sup>•–</sup>) crystallized as [Li(<sup>Dipp</sup>PSI)(Thf)<sub>2</sub>]. The samarium(III) complex [SmCp*(<sup>Dipp</sup>PDA)(Тhf)] (<b>I</b>) is formed by the reduction of <sup>Dipp</sup>PDI with samarocene [Sm<span>\\({\\text{Cp}}_{2}^{*}\\)</span>(Thf)<sub>2</sub>] (Cp* is pentamethylcyclopentadienide): both the samarium(II) cation and Cp*<sup>–</sup> anion are oxidized in the reaction. <sup>Dipp</sup>PDI does not react with similar ytterbocene. The dysprosium(III) complexes are synthesized by the ion exchange reactions between DyI<sub>3</sub>(Thf)<sub>3.5</sub> and potassium or lithium salt with the <sup>Dipp</sup>PDA<sup>2–</sup> dianion. Similar complexes [Dy(<sup>Dipp</sup>PDA)I(Thf)<sub>2</sub>] (<b>II</b><sup>Thf</sup>) and [Dy(<sup>Dipp</sup>PDA)I(Thf)(Et<sub>2</sub>O)] (<span>\\({\\mathbf{I}}{{{\\mathbf{I}}}^{{{\\text{E}}{{{\\text{t}}}_{{\\text{2}}}}{\\text{O}}}}}\\)</span>) are formed in the reactions with the potassium salt depending on the solvent used: a THF–hexane or a diethyl ether–<i>n</i>-hexane mixture, respectively. The coordination of the dysprosium cation by the π system of the conjugated fragment of the NCCN ligand is observed in <b>II</b><sup>Thf</sup>, whereas in <span>\\({\\mathbf{I}}{{{\\mathbf{I}}}^{{{\\text{E}}{{{\\text{t}}}_{{\\text{2}}}}{\\text{O}}}}}\\)</span> this coordination is absent. The reaction with Li<sub>2</sub>(<sup>Dipp</sup>PDA) affords the binary complex salt [Li(Тhf)<sub>3</sub>(Et<sub>2</sub>O)][DyI<sub>2</sub>(<sup>Dipp</sup>PDA)(Тhf)] (<b>III</b>, crystallization from a THF–Et<sub>2</sub>O mixture). The crystallization from THF gives the [Li(Тhf)<sub>4</sub>][DyI<sub>2</sub>(<sup>Dipp</sup>PDA)(Thf)] salt (<b>III'</b>) containing the same anion as <b>III</b>. The structures of all new complexes are studied by X-ray diffraction (XRD, CIF files CCDC nos. 2260307–2260313).</p>","PeriodicalId":759,"journal":{"name":"Russian Journal of Coordination Chemistry","volume":"50 1","pages":"73 - 84"},"PeriodicalIF":1.1000,"publicationDate":"2024-05-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Russian Journal of Coordination Chemistry","FirstCategoryId":"92","ListUrlMain":"https://link.springer.com/article/10.1134/S1070328423601012","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q4","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
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).
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.