10.1021/om801029k
The research investigates the reaction of Rhodium(III) porphyrins (specifically Rh(ttp)Cl) with methanol in the presence of inorganic bases at high temperatures (150 °C) to produce rhodium porphyrin methyls (Rh(ttp)CH3) with high yields (up to 87%). The study aims to understand the carbon-hydrogen bond activation chemistry of rhodium porphyrins and to explore the conditions under which methanol can react with these complexes to aid in the design of catalysts for catalytic methane oxidation. The key findings suggest that Rh(ttp)H is the key intermediate for carbon-oxygen bond cleavage, and the role of bases is to facilitate the formation of reactive intermediates and enhance reaction rates. The research concludes that to achieve efficient rhodium porphyrin-based methane oxidation, it would be necessary to either continuously remove methanol or carry out the reaction at lower conversions. The key chemicals used in the research include Rh(ttp)Cl (rhodium(III) tetrakistolylporphyrinato chloride), methanol, various inorganic bases (such as KOH, NaOH, K2CO3, Na2CO3, Potassium bicarbonate (KHCO3), K3PO4, Potassium acetate (KOAc), and Sodium acetate (NaOAc)), and other rhodium porphyrin complexes like Rh(tpp)Cl, Rh(tmp)Cl, and Rh2(ttp)2.