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FIRST EXAMPLE OF RUTHENIUM NITROSO COMPLEXES WITH A NITROXYL RADICAL AS A LIGAND

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Abstract

First example of a nitrosoruthenium complex with a nitroxyl radical is prepared by the interaction of Na2RuNOCl5 with 2-(3-pyridyl)-4,4,5,5-tetramethyl-4,5-dihydro-l-H-imidazole-1-oxyl-3-N-oxide (L) in acetonitrile at 85°C. The reaction product is the Na[RuNOCl4L] monosubstituted complex where the nitroxyl radical is coordinated by the nitrogen atom of the pyridine ring and occupies a cis position with respect to the nitroso group. The EPR data show that the spin density distribution in the radical almost does not change upon the coordination. The combination of electronic spectroscopy and density functional theory (DFT) data show that transitions at 500-700 nm are determined by the intraligand electron transfer in the nitroxide radical and by the electron transfer from the nitroxyl radical to the orbitals of the Ru–NO fragment.

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Funding

This work was funded by the Russian Science Foundation, project 22-23-00407 (synthesis, X-ray diffraction analysis, and quantum chemical calculations) and by the Ministry of Education and Science of the Russian Federation, project 121031700315-2 (EPR experiment and EPR spectra simulations).

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Authors and Affiliations

  1. Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia

    G. A. Kostin, N. V. Kuratieva & V. A. Nadolinny

  2. International Tomography Center, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia

    S. E. Tolstikov & V. I. Ovcharenko

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  1. G. A. Kostin
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  2. S. E. Tolstikov
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  3. N. V. Kuratieva
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  4. V. A. Nadolinny
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Correspondence to G. A. Kostin.

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Russian Text © The Author(s), 2023, published in Zhurnal Strukturnoi Khimii, 2023, Vol. 64, No. 2, 105395.https://doi.org/10.26902/JSC_id105395

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Kostin, G.A., Tolstikov, S.E., Kuratieva, N.V. et al. FIRST EXAMPLE OF RUTHENIUM NITROSO COMPLEXES WITH A NITROXYL RADICAL AS A LIGAND. J Struct Chem 64, 169–178 (2023). https://doi.org/10.1134/S0022476623020014

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