A Self‐Separating Multiphasic System for Catalytic Hydrogenation of CO(2) and CO(2)‐Derivatives to Methanol

Catalytic conversion of CO(2) and hydrogen to methanol was achieved in a self‐separating multiphasic system comprising the tailor‐made complex [Ru(CO)ClH(MACHO‐C(12))] (MACHO‐C(12)=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 CO(2) to methanol. The polar products MeOH or MeOH/H(2)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 CO(2), the catalyst phase was recycled over ten subsequent runs, reaching a total turnover number to MeOH of 19200 with an average selectivity of 96 %.