pH Changes That Induce an Axial Ligand Effect on Nonheme Iron(IV) Oxo Complexes with an Appended Aminopropyl Functionality
| Autor: | Reza Latifi, Kwame S. Glinton, Laleh Tahsini, Sam P. de Visser, Elena V. Rybak-Akimova, Jennifer L. Minnick, Wanhua Ye, Taryn D. Palluccio |
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| Rok vydání: | 2021 |
| Předmět: |
Olefin fiber
Molecular Structure Ligand Protonation Hydrogen-Ion Concentration Ligands Catalysis Inorganic Chemistry Oxygen chemistry.chemical_compound chemistry Cyclooctene Polymer chemistry Reactivity (chemistry) Amine gas treating Macrocyclic ligand Physical and Theoretical Chemistry Density Functional Theory Iron Compounds |
| Zdroj: | Inorganic chemistry. 60(18) |
| ISSN: | 1520-510X |
| Popis: | Nonheme iron enzymes often utilize a high-valent iron(IV) oxo species for the biosynthesis of natural products, but their high reactivity often precludes structural and functional studies of these complexes. In this work, a combined experimental and computational study is presented on a biomimetic nonheme iron(IV) oxo complex bearing an aminopyridine macrocyclic ligand and its reactivity toward olefin epoxidation upon changes in the identity and coordination ability of the axial ligand. Herein, we show a dramatic effect of the pH on the oxygen-atom-transfer (OAT) reaction with substrates. In particular, these changes have occurred because of protonation of the axial-bound pendant amine group, where its coordination to iron is replaced by a solvent molecule or anionic ligand. This axial ligand effect influences the catalysis, and we observe enhanced cyclooctene epoxidation yields and turnover numbers in the presence of the unbound protonated pendant amine group. Density functional theory studies were performed to support the experiments and highlight that replacement of the pendant amine with a neutral or anionic ligand dramatically lowers the rate-determining barriers of cyclooctene epoxidation. The computational work further establishes that the change in OAT is due to electrostatic interactions of the pendant amine cation that favorably affect the barrier heights. |
| Databáze: | OpenAIRE |
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