{"title":"结构研究，理论DFT, Hirshfeld表面分析和催化3,5- dtbc氧化两个钴(ii)配合物与氨基脲希夫碱配体","authors":"Manas Chowdhury, Niladri Biswas, Sandeepta Saha, Ennio Zangrando, Corrado Rizzoli, Nayim Sepay, Chirantan Roy Choudhury","doi":"10.1007/s11243-023-00523-0","DOIUrl":null,"url":null,"abstract":"<div><p>Two novel cobalt(<span>ii</span>) complexes [Co(HL<sup>1</sup>)<sub>2</sub>](NO<sub>3</sub>)<sub>2</sub>.2.5H<sub>2</sub>O (<b>1</b>) and [Co(HL<sup>2</sup>)<sub>2</sub>](NO<sub>3</sub>)<sub>2</sub> (<b>2</b>) (where HL<sup>1</sup> = (E)-2-(1-(pyridin-2-yl)ethylidene)hydrazine-1-carboxamide and HL<sup>2</sup> = (E)-2-(pyridin-2-ylmethylene)hydrazine-1-carboxamide) have been synthesized and structurally characterized by spectroscopic techniques and single-crystal diffraction analysis. The complexes are close comparable with metals exhibiting the expected distorted octahedral geometry being chelated by two semicarbazone ligands via NNO donor set. The catecholase-like activity of complexes <b>1</b> and <b>2</b> was evaluated by using 3,5-di-tert-butylcatecholas substrate. The results showed that both the complexes are effective catalysts with <i>K</i><sub>cat</sub> values of 762 and 562, respectively. Theoretical DFT study and Hirschfeld surface analyses were also carried out to reveal the nature of intermolecular contacts and to integrate experimental observations.\n</p><h3>Graphical abstract</h3><p>\nTwo novel cobalt(<span>ii</span>) complexes [Co(H<i>L</i><sup><i>1</i></sup>)<sub>2</sub>](NO<sub>3</sub>)<sub>2</sub>.2.5H<sub>2</sub>O (<b>1</b>) and [Co(H<i>L</i><sup><i>2</i></sup>)<sub>2</sub>](NO<sub>3</sub>)<sub>2</sub> (<b>2</b>) have been synthesized and structurally characterized by spectroscopic techniques and single-crystal diffraction analysis. The complexes are nearly akin with metals exhibiting the expected distorted octahedral geometry being chelated by two semicarbazone ligands via NNO donor set. The catecholase-like activity of complexes <b>1</b> and <b>2</b> was evaluated by using 3,5-DTBC as substrate. The result confirmed the formation of quinone or 3,5-DTBQ derivative and indicates that the complexes exhibit noticeable catalytic activity with <i>K</i><sub>cat</sub> values of 762 and 562, respectively. Theoretical DFT study and Hirschfeld surface analyses were also performed to reveal the nature of intermolecular contacts and to integrate experimental findings.</p>\n <figure><div><div><div><picture><source><img></source></picture></div></div></div></figure>\n </div>","PeriodicalId":803,"journal":{"name":"Transition Metal Chemistry","volume":null,"pages":null},"PeriodicalIF":1.6000,"publicationDate":"2023-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Structural investigation, theoretical DFT, Hirshfeld surface analysis and catalytic behaviour towards 3,5-DTBC oxidation of two cobalt(ii) complexes with semicarbazone Schiff base ligands\",\"authors\":\"Manas Chowdhury, Niladri Biswas, Sandeepta Saha, Ennio Zangrando, Corrado Rizzoli, Nayim Sepay, Chirantan Roy Choudhury\",\"doi\":\"10.1007/s11243-023-00523-0\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>Two novel cobalt(<span>ii</span>) complexes [Co(HL<sup>1</sup>)<sub>2</sub>](NO<sub>3</sub>)<sub>2</sub>.2.5H<sub>2</sub>O (<b>1</b>) and [Co(HL<sup>2</sup>)<sub>2</sub>](NO<sub>3</sub>)<sub>2</sub> (<b>2</b>) (where HL<sup>1</sup> = (E)-2-(1-(pyridin-2-yl)ethylidene)hydrazine-1-carboxamide and HL<sup>2</sup> = (E)-2-(pyridin-2-ylmethylene)hydrazine-1-carboxamide) have been synthesized and structurally characterized by spectroscopic techniques and single-crystal diffraction analysis. The complexes are close comparable with metals exhibiting the expected distorted octahedral geometry being chelated by two semicarbazone ligands via NNO donor set. The catecholase-like activity of complexes <b>1</b> and <b>2</b> was evaluated by using 3,5-di-tert-butylcatecholas substrate. The results showed that both the complexes are effective catalysts with <i>K</i><sub>cat</sub> values of 762 and 562, respectively. Theoretical DFT study and Hirschfeld surface analyses were also carried out to reveal the nature of intermolecular contacts and to integrate experimental observations.\\n</p><h3>Graphical abstract</h3><p>\\nTwo novel cobalt(<span>ii</span>) complexes [Co(H<i>L</i><sup><i>1</i></sup>)<sub>2</sub>](NO<sub>3</sub>)<sub>2</sub>.2.5H<sub>2</sub>O (<b>1</b>) and [Co(H<i>L</i><sup><i>2</i></sup>)<sub>2</sub>](NO<sub>3</sub>)<sub>2</sub> (<b>2</b>) have been synthesized and structurally characterized by spectroscopic techniques and single-crystal diffraction analysis. The complexes are nearly akin with metals exhibiting the expected distorted octahedral geometry being chelated by two semicarbazone ligands via NNO donor set. The catecholase-like activity of complexes <b>1</b> and <b>2</b> was evaluated by using 3,5-DTBC as substrate. The result confirmed the formation of quinone or 3,5-DTBQ derivative and indicates that the complexes exhibit noticeable catalytic activity with <i>K</i><sub>cat</sub> values of 762 and 562, respectively. Theoretical DFT study and Hirschfeld surface analyses were also performed to reveal the nature of intermolecular contacts and to integrate experimental findings.</p>\\n <figure><div><div><div><picture><source><img></source></picture></div></div></div></figure>\\n </div>\",\"PeriodicalId\":803,\"journal\":{\"name\":\"Transition Metal Chemistry\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":1.6000,\"publicationDate\":\"2023-03-20\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Transition Metal Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://link.springer.com/article/10.1007/s11243-023-00523-0\",\"RegionNum\":4,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q3\",\"JCRName\":\"CHEMISTRY, INORGANIC & NUCLEAR\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Transition Metal Chemistry","FirstCategoryId":"92","ListUrlMain":"https://link.springer.com/article/10.1007/s11243-023-00523-0","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
Structural investigation, theoretical DFT, Hirshfeld surface analysis and catalytic behaviour towards 3,5-DTBC oxidation of two cobalt(ii) complexes with semicarbazone Schiff base ligands
Two novel cobalt(ii) complexes [Co(HL1)2](NO3)2.2.5H2O (1) and [Co(HL2)2](NO3)2 (2) (where HL1 = (E)-2-(1-(pyridin-2-yl)ethylidene)hydrazine-1-carboxamide and HL2 = (E)-2-(pyridin-2-ylmethylene)hydrazine-1-carboxamide) have been synthesized and structurally characterized by spectroscopic techniques and single-crystal diffraction analysis. The complexes are close comparable with metals exhibiting the expected distorted octahedral geometry being chelated by two semicarbazone ligands via NNO donor set. The catecholase-like activity of complexes 1 and 2 was evaluated by using 3,5-di-tert-butylcatecholas substrate. The results showed that both the complexes are effective catalysts with Kcat values of 762 and 562, respectively. Theoretical DFT study and Hirschfeld surface analyses were also carried out to reveal the nature of intermolecular contacts and to integrate experimental observations.
Graphical abstract
Two novel cobalt(ii) complexes [Co(HL1)2](NO3)2.2.5H2O (1) and [Co(HL2)2](NO3)2 (2) have been synthesized and structurally characterized by spectroscopic techniques and single-crystal diffraction analysis. The complexes are nearly akin with metals exhibiting the expected distorted octahedral geometry being chelated by two semicarbazone ligands via NNO donor set. The catecholase-like activity of complexes 1 and 2 was evaluated by using 3,5-DTBC as substrate. The result confirmed the formation of quinone or 3,5-DTBQ derivative and indicates that the complexes exhibit noticeable catalytic activity with Kcat values of 762 and 562, respectively. Theoretical DFT study and Hirschfeld surface analyses were also performed to reveal the nature of intermolecular contacts and to integrate experimental findings.
期刊介绍：
Transition Metal Chemistry is an international journal designed to deal with all aspects of the subject embodied in the title: the preparation of transition metal-based molecular compounds of all kinds (including complexes of the Group 12 elements), their structural, physical, kinetic, catalytic and biological properties, their use in chemical synthesis as well as their application in the widest context, their role in naturally occurring systems etc.
Manuscripts submitted to the journal should be of broad appeal to the readership and for this reason, papers which are confined to more specialised studies such as the measurement of solution phase equilibria or thermal decomposition studies, or papers which include extensive material on f-block elements, or papers dealing with non-molecular materials, will not normally be considered for publication. Work describing new ligands or coordination geometries must provide sufficient evidence for the confident assignment of structural formulae; this will usually take the form of one or more X-ray crystal structures.
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