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

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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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Acknowledgements

The authors thank the National Science Foundation (grant CHE-1726630) and the University of Oklahoma for funds to purchase the X-ray instrument and computers. The authors also thank the Fitchburg State University Special Projects Grant (grant T65-1230-T00-FCIN) and Fitchburg State University for funds for this project.

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Authors and Affiliations

  1. Biology and Chemistry Department, Fitchburg State University, 160 Pearl St, Fitchburg, MA, 01420, USA

    Dennis Awasabisah & Jack F. Gangemi

  2. Department of Chemistry and Biochemistry, Stephenson Life Science Research Center, University of Oklahoma, 101 Stephenson Parkway, Norman, OK, 73019, USA

    Douglas R. Powell

  3. Gustaf H. Carlson School of Chemistry, Arthur M. Sackler Sciences Center, 950 Main Street, Worcester, MA, 01610, USA

    Guoxing Lin

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Contributions

D.A. performed experiments and wrote the main text of the manuscript. J.F.G. performed experiments and reviewed the manuscript. D.R.P. collected X-ray data, wrote the report and reviewed the manuscript. G.L. collected NMR data and reviewed the manuscript.

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Correspondence to Dennis Awasabisah.

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Awasabisah, D., Gangemi, J.F., Powell, D.R. et al. Preparation, characterization and electrochemical properties of ruthenium carbonyl octaethylporphyrins with axial quinoline and quinine ligands. Transit Met Chem 49, 75–86 (2024). https://doi.org/10.1007/s11243-023-00563-6

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