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

IF 16.4 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Accounts of Chemical Research 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.

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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

Accounts of Chemical Research 化学-化学综合

CiteScore

31.40

自引率

1.10%

发文量

312

审稿时长

2 months

期刊介绍： Accounts of Chemical Research presents short, concise and critical articles offering easy-to-read overviews of basic research and applications in all areas of chemistry and biochemistry. These short reviews focus on research from the author’s own laboratory and are designed to teach the reader about a research project. In addition, Accounts of Chemical Research publishes commentaries that give an informed opinion on a current research problem. Special Issues online are devoted to a single topic of unusual activity and significance. Accounts of Chemical Research replaces the traditional article abstract with an article "Conspectus." These entries synopsize the research affording the reader a closer look at the content and significance of an article. Through this provision of a more detailed description of the article contents, the Conspectus enhances the article's discoverability by search engines and the exposure for the research.