Abstract: Manganese(IV) species play an essential role in natural photoredox processes, making the development of artificial biomimetic catalysts a promising goal, which is, however, complicated by the lack of stable and soluble Mn(IV) complexes. Cyclic tris(hydroxylamine) ligands were recently shown to stabilize atypical +4 oxidation states for a variety of 3d metals due to a strong σ-donating ability of three deprotonated N–OH moieties. Here, we report a comprehensive study of manganese coordination chemistry with the 1,4,6,10-tetraazaadamantane-based tris(hydroxylamine) ligand (TAAD). A series of mono- and dinuclear Mn(IV)–TAAD complexes were obtained and studied by SC-XRD analysis, HRMS, NMR (Evans method), UV–Vis spectroscopy, cyclic voltammetry, and DFT calculations. The TAAD ligand was found to stabilize [Mn2(μ-OR)3]-dimeric motifs uncommon in Mn(IV) chemistry. These dinuclear motifs were shown to disassemble into mononuclear species upon treatment with chelating N-ligands. Mononuclear Mn(IV)–TAAD complexes exhibited photocatalytic activity in the oxidative azidation/ring-opening of 1-arylcyclohexenes with TMSN3 and molecular oxygen.

Cite: Sinyushin K.I. , Golovanov I.S. , Ushakov P.Y. , Lesnikov V.K. , Nelyubina Y.V. , Sukhorukov A.Y.
Unlocking Coordination Chemistry and Photocatalytic Activity of Mn(IV) Complexes with 1,4,6,10-Tetraazaadamantane-Based Tris-Hydroxylamine Ligand TAAD
Inorganic Chemistry. 2026. Т.65. №36. С.21282-21293. DOI: 10.1021/acs.inorgchem.6c03588 WOS Scopus OpenAlex

Dates:

Submitted:	Jul 9, 2026
Accepted:	Aug 21, 2026
Published online:	Sep 1, 2026

Identifiers:

≡ Web of science:	WOS:001867318800001
≡ Scopus:	2-s2.0-105050380643
≡ OpenAlex:	W7154123178

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