A dual theoretical-experimental study of Iron complexing with N-ligand: understand and design a catalyst
Iron is a ubiquitous element, present in organic and inorganic compounds, in nature and inside our bodies, for example, in hemoglobin and siderophores. From an inorganic chemistry standpoint, iron is a fascinating element found in variable oxidation and spin states depending on the nature of the bin...
Guardado en:
| Autor principal: | |
|---|---|
| Formato: | bachelorThesis |
| Lenguaje: | eng |
| Publicado: |
2021
|
| Materias: | |
| Acceso en línea: | http://repositorio.yachaytech.edu.ec/handle/123456789/342 |
| Etiquetas: |
Agregar Etiqueta
Sin Etiquetas, Sea el primero en etiquetar este registro!
|
Agregar Etiqueta | Sumario: | Iron is a ubiquitous element, present in organic and inorganic compounds, in nature and inside our bodies, for example, in hemoglobin and siderophores. From an inorganic chemistry standpoint, iron is a fascinating element found in variable oxidation and spin states depending on the nature of the binding ligands showing exciting properties.jajaja1 N-containing ligands are particularly interesting as they can stabilize even iron (IV) or iron (V) through different geometries. The affinity of nonheme ligands with iron already showed a specific affinity for nitrogen atoms, which implies a direct relationship between the number of bonds in a complex and the nitrogen content. The binding nature, ionic or covalent, is one critical aspect influencing iron properties and reactivity. In this quest of understanding, theoretical and computational chemistry have been particularly efficient.2 In this work, the theoretical study of the energetic factors that influence the catalytic effect in the oxidative dehydrogenation reaction of an iron compound coordinated with a nitrogenated ligand was developed. These reactions are very interesting because of their exothermic characteristics and their presence in fundamental reactions like alkene production from alkanes or amino acid synthesis.3,4 In this work, we demonstrate that the complex promotes the oxidation of the coordinated ligand, which contributes to form an imine from an amine through the influence of the transition metal. The metallic Fe3+ center coordinated with 1,9-bis(2’-pyridyl)-2,5,8-triazanonane or 1,9-bis(3’-pyridyl)-2,5,8-triazanonane ligands show a highly different behavior, not only in conformation but also in catalytic response. Moreover, the experimental results illustrated in the literature are supported by the theoretical results obtained.5,6 Through DFT studies, the reaction mechanism was studied to explain the observed differences between both complexes. Furthermore, the mechanisms were probed under different solvents' actions to estimate which condition would favor oxidative dehydrogenation, showing a higher affinity for water. And finally, the theoretical studies allowed us not only to explain but also to design additional modifications of the ligands, which will be tested to predict its catalytic activity. 7 |
|---|