A DFT study on the C–H oxidation reactivity of Fe(iv)–oxo species with N4/N5 ligands derived from l-proline

Abstract

The hydroxylation of hexane by two FeIVO complexes bearing a pentadentate ligand (N5, Pro3Py) and a tetradentate ligand (N4, Pro2PyBn) derived from l-proline was studied by DFT calculations.

Entropic influence on the generation of Fe(iv)O species at mononuclear Fe(ii) sites in metal–organic frameworks

“…[28][29][30][31][32] Solid-state Fe(IV)O systems have been also investigated for their potential to store methane in the case of MOF74, 33 NO adsorption in Al-rich beta zeolites 34 and in MOFs, 35 NO and N 2 O reduction by NH 3 within the framework of the zeolite Fe-BEA, [36][37][38] and the decomposition of nitrous oxide (N 2 O) in the zeolites Fe-FER, Fe-BEA, and Fe-MFI. 39,40 Whereas much is known about the generation and reactivity of Fe(IV)oxo in biochemistry, biomimetic chemistry and solution chemistry, [41][42][43][44][45][46][47] the study of these species supported by inorganic crystalline materials is still in its infancy. In particular, the generation of a ferryl group in the solid state and its regeneration as this species is consumed during a catalytic oxidation process, remain to be addressed.…”

“…Whereas much is known about the generation and reactivity of Fe( iv )oxo in biochemistry, biomimetic chemistry and solution chemistry, 41–47 the study of these species supported by inorganic crystalline materials is still in its infancy. In particular, the generation of a ferryl group in the solid state and its regeneration as this species is consumed during a catalytic oxidation process, remain to be addressed.…”

Catalytic properties of the ferryl ion in the solid state: a computational review

“…To date, the vast majority of the studies on Fe(IV)O systems have focused on gas phase or solvated systems, with a recent emphasis on high-spin complexes, [24][25][26][27][28][29][30] whereas far less is known about their catalytic activity in the solid state. A limited number of theoretical studies have been published very recently to investigate, e.g., the oxidation of methane and ethane 10,[31][32][33][34][35][36][37][38][39] in metal-organic frameworks (MOFs), of benzene on graphene, 40 of CO with N 2 O through an oriented external electric field in the MOF Fe 3 (btc) 2 41 and of methane [42][43][44][45][46][47][48] and propane 49 in zeolites.…”

“…To date, the vast majority of the studies on Fe( iv )O systems have focused on gas phase or solvated systems, with a recent emphasis on high-spin complexes, 24–30 whereas far less is known about their catalytic activity in the solid state. A limited number of theoretical studies have been published very recently to investigate, e.g.…”