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Reactivity difference in the oxidative nucleophilic reaction of peroxonickel(III) intermediates with open-chain and macrocyclic systems
- Reactivity difference in the oxidative nucleophilic reaction of peroxonickel(III) intermediates with open-chain and macrocyclic systems
- Yun, Seonggeun; Kwon, Nam; Kim, Seonghan; Jeong, Donghyun; Ohta, Takehiro; Cho, Jaeheung
- DGIST Authors
- Cho, Jaeheung
- Issue Date
- Inorganic Chemistry Frontiers, 6(8), 2112-2117
- Article Type
- MONONUCLEAR COPPER; ACTIVATION; COMPLEXES; STABILITY; APPROXIMATION; LIGANDS; BEARING; ENERGY; MODEL; CYSTEINE DIOXYGENASE
- A peroxonickel(iii) complex bearing the Me6-trien ligand, an open-chain analogue of the macrocyclic 12-TMC ligand, was synthesized and characterized by several physical methods, such as UV-vis, resonance Raman, ESI-MS and EPR. Density functional theory calculations provide geometric and electronic configurations of peroxonickel(iii) complexes. The reactivity of the peroxonickel(iii) intermediate was examined in oxidative nucleophilic reactions (e.g., aldehyde deformylation). By comparing the reactivities of the open-chain and macrocyclic peroxonickel(iii) complexes under identical reaction conditions, we were able to demonstrate that the open-chain peroxonickel(iii) complex is much more reactive than the macrocyclic analogue in aldehyde deformylation. This result provides intriguing aspects of the reactivity differences for open-chain vs. macrocyclic systems of metal complexes. © 2019 the Partner Organisations.
- Royal Society of Chemistry
- Related Researcher
Biomimetic Materials Laboratory
Biomimetics; Metalloenzymes; Nitric Oxide Suppliers in Brain; Biomimetic Materials in Life
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- Department of Emerging Materials ScienceBiomimetic Materials Laboratory1. Journal Articles
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