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Synthesis and Characterization of Mn(II) Complexes based on Amidic Ligands with Different Substituents and the Study of their Crystal Packing and the Catalytic Activity of these Complexes in Olefin Epoxidation Reactions with Dioxygen

Ghanbarpour, Alireza | 2014

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  1. Type of Document: M.Sc. Thesis
  2. Language: Farsi
  3. Document No: 45805 (03)
  4. University: Sharif University of Technology
  5. Department: Chemistry
  6. Advisor(s): Bagherzadeh, Mojtaba; Khavasi, Hamid Reza
  7. Abstract:
  8. In this study, a series of manganese(II) complexes based on amidic ligand, N-phenyl picolinamide, containing methoxy, methyl, nitro, and fluorine substituents were synthesized and the crystal structures of some of which were determined and some others were extracted from Cambridge Structural Database. The crystal packing of these compounds was interpreted and evaluated by Hirshfeld surface analysis. By considering this fact that the coordination region of some of these complexes involving: without substituent, methoxy, methyl, and fluorine substituents is remained fixed, by changing the substituent, these complexes were utilized for evaluating the effect of substituents on Mukaiyama-Yamada catalytic epoxidation reactions. The first evaluation of the effect of substituents on the central metal was carried out by DFT calculation and Mulliken charge calculation with the basis set of UB3LYP/6-311G (d,p) for any atoms except for manganese and the basis set of LANL2DZdp-ECP for manganese atom, which showed the less effect of substituents on the central metal. The catalytic activity of these complexes, in Mukaiyama epoxidation reaction, by cyclohexene as a substrate, isobuthyraldehye as a co-reagent, and dioxygen as an oxidant was measured and was comparedto one another at the initial times of the reaction. The results illustrated that the existence of electron withdrawing groups relatively can enhance the amount of conversion percentages in comparison to electron releasing groups. Then, the catalytic activity of binuclear Mn(II) complex based on nitro substituted amidic ligand, by the same conditions as other complexes, was studied. Studies showed that this complex has a high ability to epoxidize cyclic olefins in mild conditions, in comparison to its peers, and especially shows a high conversion and epoxide selectivity for cyclohexene. By studying the substituent effect,the effect of nitro group can be considered as one of the potential reasons for understanding the high catalytic activity of this complex
  9. Keywords:
  10. Manganese Complex ; Catalytic Epoxidation ; Olefins Epoxidation ; Substituent Effect ; Aerobic Epoxidation ; Crystal Packing

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