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Reactivity difference in the oxidative nucleophilic reaction of peroxonickel(III) intermediates with open-chain and macrocyclic systems

Title
Reactivity difference in the oxidative nucleophilic reaction of peroxonickel(III) intermediates with open-chain and macrocyclic systems
Authors
Yun, SeonggeunKwon, NamKim, SeonghanJeong, DonghyunOhta, TakehiroCho, Jaeheung
DGIST Authors
Cho, Jaeheung
Issue Date
2019-08
Citation
Inorganic Chemistry Frontiers, 6(8), 2112-2117
Type
Article
Article Type
Article
Keywords
MONONUCLEAR COPPERACTIVATIONCOMPLEXESSTABILITYAPPROXIMATIONLIGANDSBEARINGENERGYMODELCYSTEINE DIOXYGENASE
ISSN
2052-1553
Abstract
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.
URI
http://hdl.handle.net/20.500.11750/10445
DOI
10.1039/C9QI00465C
Publisher
Royal Society of Chemistry
Related Researcher
  • Author Cho, Jaeheung Biomimetic Materials Laboratory
  • Research Interests Biomimetics; Metalloenzymes; Nitric Oxide Suppliers in Brain; Biomimetic Materials in Life
Files:
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Collection:
Department of Emerging Materials ScienceBiomimetic Materials Laboratory1. Journal Articles


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