Shalini Rangarajan , Owen A. Beaumont , Maravanji S. Balakrishna , Glen B. Deacon , Victoria L. Blair
{"title":"亚胺双(四苯基膦)镧系(III)配合物：通过氧化原溶解和氧化还原转金属化/原溶解合成、结构研究和 Hirshfeld 表面分析","authors":"Shalini Rangarajan , Owen A. Beaumont , Maravanji S. Balakrishna , Glen B. Deacon , Victoria L. Blair","doi":"10.1016/j.ica.2024.122385","DOIUrl":null,"url":null,"abstract":"<div><div>Redox protolysis of [YbCp<sub>2</sub>(dme)] (dme = 1,2-dimethoxyethane) by imidotetraphenyldiphosphinate, ({Ph<sub>2</sub>PO}<sub>2</sub>NH) <strong>LH</strong> yields [YbCp{(Ph<sub>2</sub>PO)<sub>2</sub>N}<sub>2</sub>}(MeCN)] <strong>1</strong> and [Yb{(Ph<sub>2</sub>PO)<sub>2</sub>N}<sub>3</sub>] <strong>2</strong> with the last also obtained by oxidative protolysis of Yb(C<sub>6</sub>F<sub>5</sub>)<sub>2</sub>. The complexes [Ln{(Ph<sub>2</sub>PO)<sub>2</sub>N}<sub>3</sub>] ((Ln = Yb <strong>2</strong>, Er <strong>3</strong>, Gd <strong>4</strong>), [Sm{(Ph<sub>2</sub>PO)<sub>2</sub>N}<sub>3</sub>(MeCN)<sub>3</sub>] <strong>5</strong> and [Nd{(Ph<sub>2</sub> PO)<sub>2</sub>N}<sub>3</sub>] <strong>6</strong> have all been prepared by redox transmetallation/protolysis reactions between Yb, Er, Gd, Sm or Nd metals, bispentafluorophenylmercury and proligand <strong>LH</strong>. Complex <strong>1</strong> is formally eight coordinate with an acetonitrile, cyclopentadienyl (Cp) and two chelating <em>O</em>,<em>O</em>′-(Ph<sub>2</sub>PO)<sub>2</sub>N ligands, with the MeCN <em>trans</em> to the Cp ring. Complexes <strong>2</strong> and <strong>4·</strong>C<sub>7</sub>H<sub>8</sub> are six coordinate monomers with three chelating <em>O</em>,<em>O</em>′ diphosphinate ligands. By contrast <strong>5</strong> is a highly symmetrical nine-coordinate monomer with three acetonitrile and three chelating <em>O</em>,<em>O</em>′-<strong>L</strong> ligands. The three-dimensional Hirshfeld surface (3D-HS) analysis and the two-dimensional fingerprint plots (2D-FP) were quantified for different intermolecular interactions in complexes <strong>2</strong> and <strong>4</strong>.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"574 ","pages":"Article 122385"},"PeriodicalIF":2.7000,"publicationDate":"2024-09-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Imidobis(tetraphenylphosphinato)lanthanoid(III) complexes: Synthesis by oxidative protolysis, and redox transmetallation/protolysis, structural studies and Hirshfeld surface analysis\",\"authors\":\"Shalini Rangarajan , Owen A. Beaumont , Maravanji S. Balakrishna , Glen B. Deacon , Victoria L. Blair\",\"doi\":\"10.1016/j.ica.2024.122385\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>Redox protolysis of [YbCp<sub>2</sub>(dme)] (dme = 1,2-dimethoxyethane) by imidotetraphenyldiphosphinate, ({Ph<sub>2</sub>PO}<sub>2</sub>NH) <strong>LH</strong> yields [YbCp{(Ph<sub>2</sub>PO)<sub>2</sub>N}<sub>2</sub>}(MeCN)] <strong>1</strong> and [Yb{(Ph<sub>2</sub>PO)<sub>2</sub>N}<sub>3</sub>] <strong>2</strong> with the last also obtained by oxidative protolysis of Yb(C<sub>6</sub>F<sub>5</sub>)<sub>2</sub>. The complexes [Ln{(Ph<sub>2</sub>PO)<sub>2</sub>N}<sub>3</sub>] ((Ln = Yb <strong>2</strong>, Er <strong>3</strong>, Gd <strong>4</strong>), [Sm{(Ph<sub>2</sub>PO)<sub>2</sub>N}<sub>3</sub>(MeCN)<sub>3</sub>] <strong>5</strong> and [Nd{(Ph<sub>2</sub> PO)<sub>2</sub>N}<sub>3</sub>] <strong>6</strong> have all been prepared by redox transmetallation/protolysis reactions between Yb, Er, Gd, Sm or Nd metals, bispentafluorophenylmercury and proligand <strong>LH</strong>. Complex <strong>1</strong> is formally eight coordinate with an acetonitrile, cyclopentadienyl (Cp) and two chelating <em>O</em>,<em>O</em>′-(Ph<sub>2</sub>PO)<sub>2</sub>N ligands, with the MeCN <em>trans</em> to the Cp ring. Complexes <strong>2</strong> and <strong>4·</strong>C<sub>7</sub>H<sub>8</sub> are six coordinate monomers with three chelating <em>O</em>,<em>O</em>′ diphosphinate ligands. By contrast <strong>5</strong> is a highly symmetrical nine-coordinate monomer with three acetonitrile and three chelating <em>O</em>,<em>O</em>′-<strong>L</strong> ligands. The three-dimensional Hirshfeld surface (3D-HS) analysis and the two-dimensional fingerprint plots (2D-FP) were quantified for different intermolecular interactions in complexes <strong>2</strong> and <strong>4</strong>.</div></div>\",\"PeriodicalId\":13599,\"journal\":{\"name\":\"Inorganica Chimica Acta\",\"volume\":\"574 \",\"pages\":\"Article 122385\"},\"PeriodicalIF\":2.7000,\"publicationDate\":\"2024-09-20\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Inorganica Chimica Acta\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S0020169324004766\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, INORGANIC & NUCLEAR\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Inorganica Chimica Acta","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0020169324004766","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
Imidobis(tetraphenylphosphinato)lanthanoid(III) complexes: Synthesis by oxidative protolysis, and redox transmetallation/protolysis, structural studies and Hirshfeld surface analysis
Redox protolysis of [YbCp2(dme)] (dme = 1,2-dimethoxyethane) by imidotetraphenyldiphosphinate, ({Ph2PO}2NH) LH yields [YbCp{(Ph2PO)2N}2}(MeCN)] 1 and [Yb{(Ph2PO)2N}3] 2 with the last also obtained by oxidative protolysis of Yb(C6F5)2. The complexes [Ln{(Ph2PO)2N}3] ((Ln = Yb 2, Er 3, Gd 4), [Sm{(Ph2PO)2N}3(MeCN)3] 5 and [Nd{(Ph2 PO)2N}3] 6 have all been prepared by redox transmetallation/protolysis reactions between Yb, Er, Gd, Sm or Nd metals, bispentafluorophenylmercury and proligand LH. Complex 1 is formally eight coordinate with an acetonitrile, cyclopentadienyl (Cp) and two chelating O,O′-(Ph2PO)2N ligands, with the MeCN trans to the Cp ring. Complexes 2 and 4·C7H8 are six coordinate monomers with three chelating O,O′ diphosphinate ligands. By contrast 5 is a highly symmetrical nine-coordinate monomer with three acetonitrile and three chelating O,O′-L ligands. The three-dimensional Hirshfeld surface (3D-HS) analysis and the two-dimensional fingerprint plots (2D-FP) were quantified for different intermolecular interactions in complexes 2 and 4.
期刊介绍：
Inorganica Chimica Acta is an established international forum for all aspects of advanced Inorganic Chemistry. Original papers of high scientific level and interest are published in the form of Articles and Reviews.
Topics covered include:
• chemistry of the main group elements and the d- and f-block metals, including the synthesis, characterization and reactivity of coordination, organometallic, biomimetic, supramolecular coordination compounds, including associated computational studies;
• synthesis, physico-chemical properties, applications of molecule-based nano-scaled clusters and nanomaterials designed using the principles of coordination chemistry, as well as coordination polymers (CPs), metal-organic frameworks (MOFs), metal-organic polyhedra (MPOs);
• reaction mechanisms and physico-chemical investigations computational studies of metalloenzymes and their models;
• applications of inorganic compounds, metallodrugs and molecule-based materials.
Papers composed primarily of structural reports will typically not be considered for publication.
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