Zahra Jafari , Elham Safaei , Andrzej Wojtczak , Constantinos D. Zeinalipour-Yazdi , Bojan Kozlevčar , Zvonko Jagličić
{"title":"双(苯酚)二胺配体催化活性 Ni(II) 复合物的合成与表征","authors":"Zahra Jafari , Elham Safaei , Andrzej Wojtczak , Constantinos D. Zeinalipour-Yazdi , Bojan Kozlevčar , Zvonko Jagličić","doi":"10.1016/j.ica.2024.122353","DOIUrl":null,"url":null,"abstract":"<div><p>A novel N,N’-dimethylethylenediamine derivative of substituted bis(phenol)diamine ligands, namely 2-(<em>tert-</em>butyl)-4-methylphenol in H<sub>2</sub>L<sup>1</sup>, was synthesized by a convenient green procedure. Nickel)II) complex [NiL<sup>1</sup>] <strong>1</strong> has been synthesized and characterized by various methods along with crystal structure determined. Ni(II) coordination center in a mononuclear complex is surrounded by two phenolate oxygen atoms and two amine nitrogen atoms of the ligand in a square planar arrangement. The magnetic susceptibility of the title complex indicates a paramagnetic behavior above 150 K, while strong ferromagnetism below 100 K. Furthermore, the cyclic voltammetry studies show two ligand-centered oxidation of the phenolate groups to phenoxyl radical and the metal-centered reduction of Ni(II) to Ni(0). The Glaser coupling reaction of phenylacetylene was also studied. A strong catalytic activity at room T in THF solvent is observed for <strong>1</strong> in the presence of zinc powder as a reducing agent. A full conversion rate was achieved after 7 h at 25 °C. The DFT analysis corroborates with the square-planar NiO<sub>2</sub>N<sub>2</sub> chromophore of <strong>1</strong> being reduced in catalytically active Ni(0) by applied Zn. The calculated Gibbs free energy of the reaction leading to the formation of the substrate Ni-complex is favorable endothermic. Most of the data for <strong>1</strong> were obtained also for the very similar previously reported [NiL<sup>2</sup>] <strong>2</strong>, with 2,4- di <em>tert-</em>butylphenol in H<sub>2</sub>L<sup>2</sup>, which were than compared.</p></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"574 ","pages":"Article 122353"},"PeriodicalIF":2.7000,"publicationDate":"2024-09-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S0020169324004444/pdfft?md5=914e4167d534a4431b4cdeb3a6f7ab3f&pid=1-s2.0-S0020169324004444-main.pdf","citationCount":"0","resultStr":"{\"title\":\"Synthesis and characterization of catalytically active Ni(II) complexes with Bis(phenol)diamine ligands\",\"authors\":\"Zahra Jafari , Elham Safaei , Andrzej Wojtczak , Constantinos D. Zeinalipour-Yazdi , Bojan Kozlevčar , Zvonko Jagličić\",\"doi\":\"10.1016/j.ica.2024.122353\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>A novel N,N’-dimethylethylenediamine derivative of substituted bis(phenol)diamine ligands, namely 2-(<em>tert-</em>butyl)-4-methylphenol in H<sub>2</sub>L<sup>1</sup>, was synthesized by a convenient green procedure. Nickel)II) complex [NiL<sup>1</sup>] <strong>1</strong> has been synthesized and characterized by various methods along with crystal structure determined. Ni(II) coordination center in a mononuclear complex is surrounded by two phenolate oxygen atoms and two amine nitrogen atoms of the ligand in a square planar arrangement. The magnetic susceptibility of the title complex indicates a paramagnetic behavior above 150 K, while strong ferromagnetism below 100 K. Furthermore, the cyclic voltammetry studies show two ligand-centered oxidation of the phenolate groups to phenoxyl radical and the metal-centered reduction of Ni(II) to Ni(0). The Glaser coupling reaction of phenylacetylene was also studied. A strong catalytic activity at room T in THF solvent is observed for <strong>1</strong> in the presence of zinc powder as a reducing agent. A full conversion rate was achieved after 7 h at 25 °C. The DFT analysis corroborates with the square-planar NiO<sub>2</sub>N<sub>2</sub> chromophore of <strong>1</strong> being reduced in catalytically active Ni(0) by applied Zn. The calculated Gibbs free energy of the reaction leading to the formation of the substrate Ni-complex is favorable endothermic. Most of the data for <strong>1</strong> were obtained also for the very similar previously reported [NiL<sup>2</sup>] <strong>2</strong>, with 2,4- di <em>tert-</em>butylphenol in H<sub>2</sub>L<sup>2</sup>, which were than compared.</p></div>\",\"PeriodicalId\":13599,\"journal\":{\"name\":\"Inorganica Chimica Acta\",\"volume\":\"574 \",\"pages\":\"Article 122353\"},\"PeriodicalIF\":2.7000,\"publicationDate\":\"2024-09-07\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://www.sciencedirect.com/science/article/pii/S0020169324004444/pdfft?md5=914e4167d534a4431b4cdeb3a6f7ab3f&pid=1-s2.0-S0020169324004444-main.pdf\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Inorganica Chimica Acta\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S0020169324004444\",\"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/S0020169324004444","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
Synthesis and characterization of catalytically active Ni(II) complexes with Bis(phenol)diamine ligands
A novel N,N’-dimethylethylenediamine derivative of substituted bis(phenol)diamine ligands, namely 2-(tert-butyl)-4-methylphenol in H2L1, was synthesized by a convenient green procedure. Nickel)II) complex [NiL1] 1 has been synthesized and characterized by various methods along with crystal structure determined. Ni(II) coordination center in a mononuclear complex is surrounded by two phenolate oxygen atoms and two amine nitrogen atoms of the ligand in a square planar arrangement. The magnetic susceptibility of the title complex indicates a paramagnetic behavior above 150 K, while strong ferromagnetism below 100 K. Furthermore, the cyclic voltammetry studies show two ligand-centered oxidation of the phenolate groups to phenoxyl radical and the metal-centered reduction of Ni(II) to Ni(0). The Glaser coupling reaction of phenylacetylene was also studied. A strong catalytic activity at room T in THF solvent is observed for 1 in the presence of zinc powder as a reducing agent. A full conversion rate was achieved after 7 h at 25 °C. The DFT analysis corroborates with the square-planar NiO2N2 chromophore of 1 being reduced in catalytically active Ni(0) by applied Zn. The calculated Gibbs free energy of the reaction leading to the formation of the substrate Ni-complex is favorable endothermic. Most of the data for 1 were obtained also for the very similar previously reported [NiL2] 2, with 2,4- di tert-butylphenol in H2L2, which were than compared.
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.