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

IF 1.6 4区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR Transition Metal Chemistry Pub Date : 2023-03-20 DOI:10.1007/s11243-023-00523-0

Manas Chowdhury, Niladri Biswas, Sandeepta Saha, Ennio Zangrando, Corrado Rizzoli, Nayim Sepay, Chirantan Roy Choudhury

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Abstract

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 K_cat 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 K_cat 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.

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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

合成了两种新型钴(ii)配合物[Co(HL1)2](NO3)2.2.5H2O(1)和[Co(HL2)2](NO3)2(2)(其中HL1 = (E)-2-(1-(吡啶-2-基)乙基)肼-1-羧酰胺和HL2 = (E)-2-(吡啶-2-基亚甲基)肼-1-羧酰胺)，并通过光谱技术和单晶衍射分析对其进行了结构表征。这些配合物与通过NNO供体集被两个缩氨基脲配体螯合的金属表现出预期的扭曲八面体几何结构非常相似。以3,5-二叔丁基儿茶酚为底物，评价了配合物1和2的儿茶酚酶样活性。结果表明，两种配合物均为有效催化剂，Kcat值分别为762和562。理论DFT研究和Hirschfeld表面分析也进行了揭示分子间接触的性质和整合实验观察。摘要合成了两种新型钴(ii)配合物[Co(HL1)2](NO3)2.2.5H2O(1)和[Co(HL2)2](NO3)2(2)，并用光谱技术和单晶衍射分析对其进行了结构表征。这些配合物几乎类似于金属，表现出预期的扭曲八面体几何形状，通过NNO供体集被两个氨基脲配体螯合。以3,5- dtbc为底物评价配合物1和2的儿茶酚酶样活性。结果证实了醌或3,5- dtbq衍生物的形成，并表明配合物具有明显的催化活性，Kcat值分别为762和562。理论DFT研究和Hirschfeld表面分析也进行了揭示分子间接触的性质和整合实验结果。

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来源期刊

Transition Metal Chemistry 化学-无机化学与核化学

CiteScore

3.60

自引率

0.00%

发文量

审稿时长

1.3 months

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.