Synthesis, characterization and catalytic activity of novel monometallic and bimetallic Mn(II) complexes with thiocarboxamide and phenanthroline ligands

IF 1.6 4区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Transition Metal Chemistry Pub Date : 2023-05-19 DOI:10.1007/s11243-023-00532-z

Hakan Ünver, Meysam Kakavand, Abdollah Neshat

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Abstract

Novel manganese(II) complexes, 1–3, involving 1,10-phenanthroline and thiocarboxamide ligands, were prepared and characterized structurally using single-crystal X-ray diffraction that revealed monometallic and bimetallic nature of the octahedral complexes. The catalytic activities of 1–3 were investigated in the oxidation of selected primary and secondary alcohols. During the optimization of the oxidation reactions, 1, a bimetallic manganese(II) complex bearing phenanthroline and bridging anthranilate showed higher activity as catalyst precursor than monometallic 2 or 3 in the oxidation of primary alcohols. The catalytic reactions were carried out in the presence of various oxidants such as molecular oxygen, hydrogen peroxide and tert-butyl hydroperoxide (TBHP) and additives such as acetic acid and imidazole. In this study, the oxidant/additive combination of TBHP and imidazole was shown to be effective for the oxidation of substrates investigated and the degree of their impact on oxidation reaction is highly dependent on a balanced ratio between them. 1 and 2 were selected as the most effective catalyst precursor under optimized reaction conditions and revealed efficient for the oxidation of selected primary and secondary alcohols, respectively.

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新型单金属和双金属硫代甲酰胺和邻菲罗啉配合物的合成、表征和催化活性

制备了新型锰(II)配合物1 - 3，涉及1,10-菲罗啉和硫代氨基甲酸乙酯配体，并利用单晶x射线衍射对其进行了结构表征，揭示了八面体配合物的单金属和双金属性质。考察了1-3对选定的伯醇和仲醇氧化的催化活性。在优化氧化反应过程中，含邻菲罗啉和桥接邻氨基苯甲酸酯的双金属锰配合物1在伯醇氧化反应中表现出比单金属2或3更高的催化前驱体活性。在分子氧、过氧化氢、过氧化叔丁基(TBHP)等氧化剂和乙酸、咪唑等助剂的存在下进行催化反应。在这项研究中，三必和二必和咪唑的氧化剂/添加剂组合被证明对所研究的底物的氧化是有效的，它们对氧化反应的影响程度高度依赖于它们之间的平衡比例。在优化的反应条件下，选择1和2作为最有效的催化剂前驱体，分别对选定的伯醇和仲醇具有较好的氧化效果。

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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.