A manganese(III) porphyrin/rhodium(III) bipyridine/formate catalyst system for the reductive activation of molecular oxygen

Abstract

A two-phase system utilizing a rhodium(III) bipyridine complex and a manganese(III) porphyrin in the presence of sodium formate for the reductive activation o f molecular oxygen and the subsequent epoxidation of alkenes is described. In this system, the reducing equivalents for the conversion of Mnffl to Mn11 are obtained from the rhodium-catalyzed oxidation of formate to carbon dioxide.

Recent Advances in Transition Metal Catalyzed Oxidation of Organic Substrates with Molecular Oxygen

“…Investigation of 5 reveals that it exists as a monomer and does not undergo dimerization through the formation of a μ-oxobridge 17a or oxidative degradation via the formation of a multinuclear μ-oxo complex 17b during the reaction processes due to steric hindrance 17c. Nolte and Gosling reported a two-phase system utilizing MnTPPCl 6 (TPP = 5,10,15,20-tetraphenylporphyrinato) and [Rh(III)bipyCp*Cl]Cl (bipy = 2,2‘-bipyridine; Cp* = η-C 5 Me 5 ) with sodium formate for the reductive activation of molecular oxygen and the subsequent epoxidation of alkenes . The reducing equivalents for the conversion of Mn III to Mn II are obtained from the rhodium-catalyzed oxidation of formate to CO 2 (Scheme ).…”

Norbornene Oxidation by Chiral Complexes Encapsulated in NaY Zeolite

“…Norbornene , and secondary alcohols , have also been oxidized in the presence of manganese-based catalysts. Less attention has been given to rhodium complexes in oxidation reactions. , These results point out the success of olefins as well as oxidation of alcohols with manganese and rhodium complexes encapsulated into the NaY zeolite. The use of inorganic porous material has been high in the oxidation of organic compounds of large molecular sizes with a bulky oxidant such as tert -butyl hydroperoxide ( t BuOOH).…”

Enhanced decomposition of dimethyl phthalate via molecular oxygen activated by Fe@Fe2O3/AC under microwave irradiation

“…Chen et al investigated the photocatalytic degradation of DMP proteins could activate molecular oxygen in metabolic reactions [16]. Inspired by this biological molecular oxygen activation process, Gosling and Nolte [17] utilized a rhodium (III) bipyridine complex and manganese (III) porphyrin to activate molecular oxygen for the epoxidation of alkenes. Rutkowska-Zbik and Witko [18] reported the modeling of the activation of molecular oxygen by the five-coordinate manganese (III) porphyrin and the subsequent hydrogen adsorption processes formed the reactive manganese (V) oxo complex.…”