Preparation, characterization and electrochemical properties of ruthenium carbonyl octaethylporphyrins with axial quinoline and quinine ligands

IF 1.6 4区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Transition Metal Chemistry Pub Date : 2023-11-21 DOI:10.1007/s11243-023-00563-6

Dennis Awasabisah, Jack F. Gangemi, Douglas R. Powell, Guoxing Lin

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Abstract

The six-coordinate ruthenium(II) porphyrin complexes (OEP)Ru(CO)(Q), (OEP = 2,3,7,8,12,13,17,18-octaethylporphyrinato dianion; Q = quinoline, Qnl (2); quinine, QN (3)) have been prepared from (OEP)Ru(CO) (1) and characterized by MS, IR, UV–visible and ¹H NMR spectroscopy. The X-ray crystal structure of 2 has been determined, which reveals quinoline coordination to Ru through the nitrogen atom. In the crystal packing of 2, the two Qnl groups of adjacent porphyrins are positioned relatively parallel to each other at a close distance of 3.30 Å, implying a relatively strong π-π interaction. The X-ray crystal structure of 1 was obtained, which revealed coordination of the water to the ruthenium center. By comparing the spectroscopic data for 1, 2 and 3, it was determined that the site of binding of QN to Ru is likely through the nitrogen atom of the quinoline moiety. The redox behavior of the complexes at a Pt working electrode studied in a CH₂Cl₂ solution with NBu₄PF₆ as support electrolyte by cyclic voltammetry revealed oxidations that are porphyrin-centered.

Graphical abstract

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轴向喹啉和奎宁配体羰基辛乙基卟啉钌的制备、表征和电化学性能

六配位钌(II)卟啉配合物(OEP)Ru(CO)(Q)， (OEP = 2,3,7,8,12,13,17,18-八烷基卟啉离子;Q =喹啉，Qnl (2);以(OEP)Ru(CO)(1)为原料制备了奎宁QN(3)，并用质谱、红外光谱、紫外可见光谱和核磁共振氢谱对其进行了表征。测定了2的x射线晶体结构，发现喹啉通过氮原子与Ru配位。在2的晶体填料中，相邻卟啉的两个Qnl基团相对平行，距离为3.30 Å，这意味着π-π相互作用相对较强。得到了1的x射线晶体结构，揭示了水与钌中心的配位。通过比较1、2和3的光谱数据，确定QN与Ru的结合位点可能是通过喹啉部分的氮原子。在以NBu4PF6为支撑电解质的CH2Cl2溶液中，用循环伏安法研究了配合物在Pt工作电极上的氧化还原行为，发现其氧化以卟啉为中心。图形抽象

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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.