A Self-Separating Multiphasic System for Catalytic Hydrogenation of CO₂ and CO₂ -Derivatives to Methanol

Catalytic conversion of CO₂ and hydrogen to methanol was achieved in a self-separating multiphasic system comprising the tailor-made complex [Ru(CO)ClH(MACHO-C₁₂ )] (MACHO-C₁₂ =bis{2-[bis(4-dodecylphenyl)phosphino]ethyl}amine) in n-decane as the catalyst phase. Effective catalyst recycling was demonstrated for the carbonate and the amine-assisted pathway from CO₂ to methanol. The polar products MeOH or MeOH/H₂ O generated from the catalytic reactions spontaneously formed a separate phase, allowing product isolation and catalyst separation without the need for any additional solvent. In the amine-assisted hydrogenation of CO₂ , the catalyst phase was recycled over ten subsequent runs, reaching a total turnover number to MeOH of 19200 with an average selectivity of 96 %.