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Ligand Architecture Perturbation Influences the Reactivity of Nonheme Iron(V)-Oxo Tetraamido Macrocyclic Ligand Complexes: A Combined Experimental and Theoretical Study
- Title
- Ligand Architecture Perturbation Influences the Reactivity of Nonheme Iron(V)-Oxo Tetraamido Macrocyclic Ligand Complexes: A Combined Experimental and Theoretical Study
- Authors
- Li X.-X.; Xue S.-S.; Lu X.; Seo M.S.; Lee Y.-M.; Kim W.-S.; Cho K.-B.; Nam W.
- Ewha Authors
- 남원우; 이용민; 서미숙; 김원석
- SCOPUS Author ID
- 남원우; 이용민; 서미숙; 김원석
- Issue Date
- 2021
- Journal Title
- Inorganic Chemistry
- ISSN
- 0020-1669
- Citation
- Inorganic Chemistry vol. 60, no. 6, pp. 4058 - 4067
- Publisher
- American Chemical Society
- Indexed
- SCIE; SCOPUS
- Document Type
- Article
- Abstract
- Iron(V)-oxo complexes bearing negatively charged tetraamido macrocyclic ligands (TAMLs) have provided excellent opportunities to investigate the chemical properties and the mechanisms of oxidation reactions of mononuclear nonheme iron(V)-oxo intermediates. Herein, we report the differences in chemical properties and reactivities of two iron(V)-oxo TAML complexes differing by modification on the "Head"part of the TAML framework; one has a phenyl group at the "Head"part (1), whereas the other has four methyl groups replacing the phenyl ring (2). The reactivities of 1 and 2 in both C-H bond activation reactions, such as hydrogen atom transfer (HAT) of 1,4-cyclohexadiene, and oxygen atom transfer (OAT) reactions, such as the oxidation of thioanisole and its derivatives, were compared experimentally. Under identical reaction conditions, 1 showed much greater reactivity than 2, such as a 102-fold decrease in HAT and a 105-fold decrease in OAT by replacing the phenyl group (i.e., 1) with four methyl groups (i.e., 2). Then, density functional theory calculations were performed to rationalize the reactivity differences between 1 and 2. Computations reproduced the experimental findings well and revealed that the replacement of the phenyl group in 1 with four methyl groups in 2 not only increased the steric hindrance but also enlarged the energy gap between the electron-donating orbital and the electron-accepting orbital. These two factors, steric hindrance and the orbital energy gap, resulted in differences in the reduction potentials of 1 and 2 and their reactivities in oxidation reactions. ©
- DOI
- 10.1021/acs.inorgchem.1c00110
- Appears in Collections:
- 자연과학대학 > 화학·나노과학전공 > Journal papers
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