Transition metal(IV) complexes of nitro-substituted 2,4,9-triazaadamantane-based tris-hydroxylamines: evidence for nitrogen α-effect on stabilization of higher oxidation states

Transition metal(IV) complexes of nitro-substituted 2,4,9-triazaadamantane-based tris-hydroxylamines: evidence for nitrogen α-effect on stabilization of higher oxidation states Full article

Journal

Dalton Transactions
ISSN: 1477-9234 , E-ISSN: 1477-9226

Output data

Year: 2025, Volume: 54, Pages: 9530-9541 Pages count : 12 DOI: 10.1039/d5dt00812c

Authors

Pospelov Evgeny V ^1,2 , Sinyushin Kirill I ^1,3 , Golovanov Ivan S ¹ , Lesnikov Vladislav K ¹ , Frolov Kirill V ⁴ , Nelyubina Yulia V ⁵ , Sukhorukov Alexey Yu ¹

Affiliations

1	Laboratory of Organic and Metal-Organic Nitrogen-Oxygen Systems (LOMONOS), N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky prospect, 47, Moscow, 119991, Russian Federation. sukhorukov@ioc.ac.ru.
2	Department of Chemistry, Higher School of Economics National Research University, Moscow, 101000, Russian Federation.
3	D. Mendeleev University of Chemical Technology of Russia, Miusskaya sq. 9, Moscow, 125047, Russian Federation.
4	A. V. Shubnikov Institute of Crystallography of the Kurchatov Complex of Crystallography and Photonics of the NRC "Kurchatov Institute", Moscow, 119333, Russian Federation.
5	A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilova str. 28, bld. 1, Moscow, 119334, Russian Federation.

7-Nitro-2,4,9-triazaadamantane-2,4,9-triols (NO2-TRIADs), new chelating tris-hydroxylamine ligands, were synthesized by a novel one-pot, four-component condensation involving nitromethane and nitrosoalkene precursors. Upon deprotonation, NO2-TRIADs form stable diamantane-like complexes with manganese, iron and nickel in atypical +4 oxidation state. These complexes were characterized by XRD analysis, NMR, Mössbauer spectroscopy, UV-Vis, FT-IR, HRMS, and elemental analysis. Theoretical analysis based on DFT calculations revealed a remarkable electron donating “α-effect” of the nitrogen atom in the N–O–M fragment that is responsible for the stabilization of the higher oxidation state of the metal in these complexes. Metal(IV) complexes of NO2-TRIADs exhibit high catalytic activity in oxidation reactions, in particular, in the aerobic conversion of thiols into disulfides (up to 98% yield) and oxidation of activated C–H bonds in diphenylmethanol and dihydroanthracene with mCPBA (up to 74% yield). In the oxidation of dihydroanthracene, a notable selectivity toward the formation of anthraquinone was achieved (anthraquinone/anthrone = 7).

Pospelov E.V. , Sinyushin K.I. , Golovanov I.S. , Lesnikov V.K. , Frolov K.V. , Nelyubina Y.V. , Sukhorukov A.Y.
Transition metal(IV) complexes of nitro-substituted 2,4,9-triazaadamantane-based tris-hydroxylamines: evidence for nitrogen α-effect on stabilization of higher oxidation states
Dalton Transactions. 2025. V.54. P.9530-9541. DOI: 10.1039/d5dt00812c WOS Scopus OpenAlex

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