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.
10.1002/chem.201101529
The research focuses on the development of a novel synthetic methodology for the preparation of C1-symmetric bis(diphenylphosphino)biphenyl ligands, which are crucial in asymmetric catalysis. The study aimed to overcome the challenges associated with the synthesis of these ligands, particularly the undesired intramolecular cyclization leading to phosphafluorene formation. The researchers successfully developed a palladium-catalyzed C–P coupling reaction that does not require additional ligands and avoids the formation of phosphafluorene in most cases. This method allows for the rapid synthesis of a variety of substituted ortho,ortho'-bis(diphenylphosphino)biphenyls in moderate-to-excellent yields and significantly reduced reaction times compared to previous methods. Key chemicals used in the process include ortho,ortho’-dihalobiphenyl precursors, diphenylphosphine (HPPh2), palladium acetate (Pd(OAc)2) as the catalyst, potassium acetate (KOAc) as the base, and N,N-dimethylacetamide (DMA) as the solvent. The study's conclusions open new pathways for the synthesis of more complex diphosphines based on C1- or C2-symmetric biaryl scaffolds and has implications for the direct synthesis of enantiomerically pure C1-symmetric biaryl-based diphosphines.