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Bioinspired oxidation of oximes to nitric oxide with dioxygen by a nonheme iron(II) complex

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Abstract

The ability of two iron(II) complexes, [(TpPh2)FeII(benzilate)] (1) and [(TpPh2)(FeII)2(NPP)3] (2) (TpPh2 = hydrotris(3,5-diphenylpyrazol-1-yl)borate, NPP-H = α-isonitrosopropiophenone), of a monoanionic facial N3 ligand in the O2-dependent oxidation of oximes is reported. The mononuclear complex 1 reacts with dioxygen to decarboxylate the iron-coordinated benzilate. The oximate-bridged dinuclear complex (2), which contains a high-spin (TpPh2)FeII unit and a low-spin iron(II)–oximate unit, activates dioxygen at the high-spin iron(II) center. Both the complexes exhibit the oxidative transformation of oximes to the corresponding carbonyl compounds with the incorporation of one oxygen atom from dioxygen. In the oxidation process, the oxime units are converted to nitric oxide (NO) or nitroxyl (HNO). The iron(II)–benzilate complex (1) reacts with oximes to afford HNO, whereas the iron(II)–oximate complex (2) generates NO. The results described here suggest that the oxidative transformation of oximes to NO/HNO follows different pathways depending upon the nature of co-ligand/reductant.

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Acknowledgements

TKP acknowledges Science and Engineering Research Board (SERB), India, for the financial support (Project: EMR/2014/000972). SB thanks the Department of Science and Technology (DST), Govt. of India, for INSPIRE fellowship, and TRL thanks the Council of Scientific and Industrial Research (CSIR), India, for a research fellowship.

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Authors and Affiliations

  1. School of Chemical Sciences, Indian Association for the Cultivation of Science, 2A & 2B Raja S. C. Mullick Road, Jadavpur, Kolkata, 700032, India

    Shrabanti Bhattacharya, Triloke Ranjan Lakshman, Subhankar Sutradhar, Chandan Kumar Tiwari & Tapan Kanti Paine

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  1. Shrabanti Bhattacharya
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  2. Triloke Ranjan Lakshman
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  3. Subhankar Sutradhar
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Correspondence to Tapan Kanti Paine.

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Supplementary material 2 (PDF 199 kb) Spectral data and crystallographic data in cif file format. CCDC 1906732 (for 2) contains the supplementary crystallographic data for this paper. These data can be obtained free of charge via http://www.ccdc.cam.ac.uk/data_request/cif or by emailing data_request@ccdc.cam.ac.uk, or by contacting The Cambridge Crystallographic Data Centre, 12, Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033

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Bhattacharya, S., Lakshman, T.R., Sutradhar, S. et al. Bioinspired oxidation of oximes to nitric oxide with dioxygen by a nonheme iron(II) complex. J Biol Inorg Chem 25, 3–11 (2020). https://doi.org/10.1007/s00775-019-01726-6

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  • DOI: https://doi.org/10.1007/s00775-019-01726-6

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