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NMR spectroscopic studies of ligand exchange in paramagnetic complexes of Co and Ni hydrometallatranes

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Abstract

Paramagnetic complexes of hydrometallatranes with Co2+ and Ni2+ were studied by high-resolution 1H and 13C NMR spectroscopy. The paramagnetic shifts of the signals in the 1H NMR spectra by ∼100 ppm downfield with respect to their position in the spectra of uncoordinated ligands were observed. A similar upfield shift by ∼400 ppm was observed in the 13C NMR spectra. Analysis showed that paramagnetic shifts are caused by the contact hyperfine or electron-nucleus interactions between the unpaired electrons and the resonating nuclei of the ligand molecules. It was found that the preferred tridentate N,O,O-state of the ligand (triethanolamine) in aqueous solutions is accompanied by the intraligand exchange, in which two out of three oxygen centers compete for coordination. Triethanolamine was found to undergo substitution with 1-methylimidazole under mild conditions with the formation of complexes of the composition M(MIm)4X2 (M = Co, Ni; X = Cl, AcO). This causes a paramagnetic shift of the signals in the 13C NMR spectra as a result of the hyperfine interaction of the MIm nuclei with the unpaired spins of the coordinating ion.

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Funding

This work was financially supported by the Russian Foundation for Basic Research and the Government of the Irkutsk Region (Project No. 20-43-380001).

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Authors and Affiliations

  1. Irkutsk National Research State Technical University, 83 ul. Lermontova, 664074, Irkutsk, Russia

    V. K. Voronov

  2. A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, 1 ul. Favorskogo, 664033, Irkutsk, Russia

    I. A. Ushakov, S. N. Adamovich & E. N. Oborina

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  1. V. K. Voronov
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  2. I. A. Ushakov
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Correspondence to I. A. Ushakov.

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Dedicated to Academician of the Russian Academy of Sciences R. Z. Sagdeev on the occasion of his 80th birthday.

Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2354–2358, December, 2021.

This paper does not contain descriptions of studies on animals or humans.

The authors declare no competing interests.

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Voronov, V.K., Ushakov, I.A., Adamovich, S.N. et al. NMR spectroscopic studies of ligand exchange in paramagnetic complexes of Co and Ni hydrometallatranes. Russ Chem Bull 70, 2354–2358 (2021). https://doi.org/10.1007/s11172-021-3352-7

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  • DOI: https://doi.org/10.1007/s11172-021-3352-7

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