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Brønsted Acids Promote Olefin Oxidations by Bioinspired Nonheme CoIII(PhIO)(OH) Complexes: A Role for Low-Barrier Hydrogen Bonds
- Title
- Brønsted Acids Promote Olefin Oxidations by Bioinspired Nonheme CoIII(PhIO)(OH) Complexes: A Role for Low-Barrier Hydrogen Bonds
- Authors
- Sun D.; Wu Z.; Zhang X.; Yang J.; Zhao Y.; Nam W.; Wang Y.
- Ewha Authors
- 남원우
- SCOPUS Author ID
- 남원우
- Issue Date
- 2023
- Journal Title
- Journal of the American Chemical Society
- ISSN
- 0002-7863
- Citation
- Journal of the American Chemical Society vol. 145, no. 10, pp. 5739 - 5749
- Publisher
- American Chemical Society
- Indexed
- SCIE; SCOPUS
- Document Type
- Article
- Abstract
- Introduction of Brønsted acids into biomimetic nonheme reactions promotes the oxidative ability of metal-oxygen complexes significantly. However, the molecular machinery of the promoted effects is missing. Herein, a comprehensive investigation of styrene oxidation by a cobalt(III)-iodosylbenzene complex, [(TQA)CoIII(OIPh)(OH)]2+ (1, TQA = tris(2-quinolylmethyl)amine), in the presence and absence of triflic acid (HOTf) was performed using density functional theory calculations. Results revealed for the first time that there is a low-barrier hydrogen bond (LBHB) between HOTf and the hydroxyl ligand of 1, which forms two valence-resonance structures [(TQA)CoIII(OIPh)(HO--HOTf)]2+ (1LBHB) and [(TQA)CoIII(OIPh)(H2O-OTf-)]2+ (1′LBHB). Due to the oxo-wall, these complexes (1LBHB and 1′LBHB) cannot convert to high-valent cobalt-oxyl species. Instead, styrene oxidation by these oxidants (1LBHB and 1′LBHB) shows novel spin-state selectivity, i.e., on the ground closed-shell singlet state, styrene is oxidized to an epoxide, whereas on the excited triplet and quintet states, an aldehyde product, phenylacetaldehyde, is formed. The preferred pathway is styrene oxidation by 1′LBHB, which is initiated by a rate-limiting bond-formation-coupled electron transfer process with an energy barrier of 12.2 kcal mol-1. The nascent PhIO-styrene-radical-cation intermediate undergoes an intramolecular rearrangement to produce an aldehyde. The halogen bond between the OH-/H2O ligand and the iodine of PhIO modulates the activity of the cobalt-iodosylarene complexes 1LBHB and 1′LBHB. These new mechanistic findings enrich our knowledge of nonheme chemistry and hypervalent iodine chemistry and will play a positive role in the rational design of new catalysts. © 2023 American Chemical Society
- DOI
- 10.1021/jacs.2c12307
- Appears in Collections:
- 자연과학대학 > 화학·나노과학전공 > Journal papers
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