| Titre : | Etude theorique de la complexation des metaux de transition par les bases de schiff |
| Auteurs : | Hanane Mezoudji, Auteur ; B. Zouchoune, Directeur de thèse |
| Type de document : | Thése doctorat |
| Editeur : | Biskra [Algérie] : Faculté des Sciences Exactes et des Sciences de la Nature et de la Vie, Université Mohamed Khider, 2010 |
| Format : | 1 vol. (119 p.) / ill.couv.ill.en coul / 29cm |
| Langues: | Français |
| Langues originales: | Français |
| Mots-clés: | Keywords: DFT,TD-DFT ; Schiff basis ; Electronic structure ; absorption ; HOMO-LUMO. . |
| Résumé : |
The quantum calculations mainly based on the theory of density functional (DFT) were shown to be essential tools in understanding of structural arrangements and the interpretation of the physico-chemical properties of organometallic buildings. Within this framework, the work carried out at the time of this thesis concerns the theoretical study of the interactions and the complexation of metals of transition with the bases of Schiff which have a particular interest because of their mode of coordination. The occupation of the OM informs us about the direction of the electronic transfers. This manuscript is divided into three chapters. The first is an introduction to the methods of calculation of quantum chemistry used into our work, as one points out rules of stability of 114 metals of transition (rule of the 18 electrons). The second chapter describes the electronic structure of the organometallic compounds of type [RuX2(EH3)2(DHA-R)] (X=Cl ou Br; E=P ou As; R=-CH3, -C6H11, C4H4N). Finally the final chapter approaches the study of the complexes of general formula [MLn(H2O)]q. The principal theoretical results obtained are presented in this memory. The complexes show transitions MLCT, IL, and LMCT in the UV-visible field. The central idea is to include and understand using the calculations carried out on these compounds using the method DFT and method TD-DFT, the nature of the chemical bond between the base of Schiff and the metal center. Calculations of DFT dependent on time indicate that the electronic excitations observed in experiments for these complexes are not due a transition HOMO towards LUMO, but with several excitations between the orbital occupied ones of lower energy and orbital vacant the highest in energy. |
| Sommaire : |
Introduction générale 1. Introduction générale……………………………………………………………………… 2 Références …………………………………………………………………………………… 4 Chapitre I Aspect théorique et méthodes de calculs I.1 Introduction……………………………………………………………………………..... 5 I.2. Rappels. L’équation de Schrödinger……………………………………………….…..... 5 I.3. Les méthodes quantiques ………………………………………………………………….. 7 I.3.1. Les méthodes Hartree-Fock ………………….………………………………….....….. 10 1.3.2.La théorie de la fonctionnelle de la densité (DFT) ……………………………………. 12 1.4. Conditions de stabilité d’un système chimique …………………………..…………….. 13 I.5. La règle des 18 électrons (ou formalisme EAN)………….……………………………... 15 Références ………………………………………………………………………………… 17 Chapitre II Étude théorique des Complexes à bases de Schiff de Ru (III) II.1. Introduction …………………………………………………………………………….. 20 II.2. L’anion de la base de Schiff (DHA-Met)……………………………………………….. 20 II.2.1. Complexes [RuX2(EH3)2(DHA-Met)]- ………………………………………………... 22 II.2.2. Propriétés optiques des complexes [RuX2(EH3)2(DHA-Met)]- ………………………. 28 II.3. L’anion de la base de Schiff (DHA-Chx) ………………………………………………. 32 II.3.1. Complexes [RuX2 (EH3)2(DHA-Chx)]- ………………………………………………. 34 II.3.2. Propriétés optiques des complexes [RuX2(EH3)2(DHA-Chx)]- ………………………. 38 II.4. L’anion de la base de Schiff (DHA-Ampy) …………………………………………….. 42 II.4.1. Complexes [RuX2(EH3)2(DHA-Ampy)]- ……………………………………………… 44 II.4.2. Propriétés optiques des complexes [RuX2(EH3)2(DHA-Ampy)]- …………………….. 48 Conclusion………………………………………………………………………….……….. 51 Références………………………….…………………………………………………..……. 53 Chapitre III Complexation de base de Schiff avec différents métaux de transition. III.1. Introduction…….………………………………………………………………………. 55 III.2. Etude des entités [ML1(H2O)2]q …..………………………………………………........ 57 - [CoL1(H2O)2] q :( q= -1 à +1)………………………………………. 57 - [NiL1(H2O)2]….…………………………………………………………………….. 63 - [CuL1(H2O)2] q :( q= -1 à +1)………………………………………… 65 - [ZnL1(H2O)2]………………………………………………………………………… 67 III .3. Propriétés optiques des complexes [ML1(H2O)2]q ……………………. 69 III.4. Etude des entité [ML2X(H2O)2]q ……………………………………………………….. 75 - [CoL2Cl(H2O)2] q :( q= -1 à +1) ............................. 76 - [NiL2Ac(H2O)2]……………………………………………………………………....78 - [CuL2Ac(H2O)2] q :( q= -1 à +1)……………………………………………………. 79 - [ZnL2Ac(H2O)2]…………………………………………………………………….. 80 III .5. Propriétés optiques des complexes [ML2X(H2O)2]q ………………………... 83 III.6. Etude des entité [ML3X(H2O)2]q ……………………………………………………….. 89 - [CoL3Cl(H2O)2] q :( q= +1 à -1)……………………………………………………. 89 - [NiL3Ac(H2O)2]……………………………………………………………………… 93 - [CuL3Ac(H2O)2] q :( q= +1 à -1)……………………………………………………. 95 - [ZnL3Ac(H2O)2]……………………………………………………………………... 97 III .7. Propriétés optiques des complexes [ML3(H2O)2X]q …………………... 99 Conclusion …………………………………………………………………………………… 105 Références …………………………………………………………………………………... 107 Conclusion générale …………………………………………………………………………. 109 Annexe………………………………………………………………………………………… 111 Résumé ……………………………………………………………………………………….. 114 |
| Type de document : | Thése doctorat |
| En ligne : | http://thesis.univ-biskra.dz/3425/1/M%C3%A9moire%20de%20Magist%C3%A8re%20Mezoudji%20Hanane.PDF |
Disponibilité (1)
| Cote | Support | Localisation | Statut |
|---|---|---|---|
| TCH/10 | Mémoire de magister | bibliothèque sciences exactes | Consultable |
