What does this research mean for the field?

The 1,4,6,10-tetraazaadamantane-based tris(hydroxylamine) ligand (TAAD) stabilizes uncommon dimeric Mn(IV) motifs that can disassemble into mononuclear species exhibiting photocatalytic activity in the oxidative azidation of 1-arylcyclohexenes. Novelty: ClaimNovelty.NOVEL_FINDING. Consensus alignment: ConsensusAlignment.NEUTRAL.

What question did this study set out to answer?

To synthesize and characterize stable, soluble manganese(IV) complexes using a rigid tris(hydroxylamine) ligand and evaluate their potential as photoredox catalysts.

September 5, 2026Inorganic ChemistryOpen Access

Unlocking Coordination Chemistry and Photocatalytic Activity of Mn(IV) Complexes with 1,4,6,10-Tetraazaadamantane-Based Tris-Hydroxylamine Ligand TAAD

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Authors

KSKirill I. SinyushinD. Mendeleyev University of Chemical Technology of Russia IGIvan S. GolovanovN.D. Zelinsky Institute of Organic Chemistry PUPavel Yu. UshakovN.D. Zelinsky Institute of Organic Chemistry

Discussion

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Implication

Experimental and computational analysis reveals stable mono- and dinuclear manganese(IV) complexes supported by a cyclic ligand, indicating viable biomimetic photoredox catalytic activity.

Key Points

To synthesize and characterize stable, soluble manganese(IV) complexes using a rigid tris(hydroxylamine) ligand and evaluate their potential as photoredox catalysts.
Synthesized mono- and dinuclear Mn(IV) complexes supported by the 1,4,6,10-tetraazaadamantane-based tris(hydroxylamine) ligand (TAAD).
Characterized structural and electronic features using single-crystal X-ray diffraction, high-resolution mass spectrometry, Evans NMR, UV–Vis spectroscopy, cyclic voltammetry, and density functional theory calculations.
Evaluated photocatalytic reactivity in the oxidative azidation and ring-opening of 1-arylcyclohexenes in the presence of trimethylsilyl azide and oxygen.
Demonstrated that the TAAD framework stabilizes unusual triply alkoxo-bridged dinuclear [Mn2(μ-OR)3] motifs that cleanly disassemble into mononuclear species upon exposure to chelating N-ligands.
Established that the resulting mononuclear Mn(IV)–TAAD complexes serve as active photocatalysts for the aerobic oxidative azidation and ring-opening of cyclic alkenes.

Cite This Study

Sinyushin et al. (2026) studied this question.

synapsesocial.com/papers/6a9bd3726b95aff0620eaa54 https://doi.org/10.1021/acs.inorgchem.6c03588

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Implication

Experimental and computational analysis reveals stable mono- and dinuclear manganese(IV) complexes supported by a cyclic ligand, indicating viable biomimetic photoredox catalytic activity.

Unlocking Coordination Chemistry and Photocatalytic Activity of Mn(IV) Complexes with 1,4,6,10-Tetraazaadamantane-Based Tris-Hydroxylamine Ligand TAAD

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Cite This Study

Unlocking Coordination Chemistry and Photocatalytic Activity of Mn(IV) Complexes with 1,4,6,10-Tetraazaadamantane-Based Tris-Hydroxylamine Ligand TAAD

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