Sol–gel derived hybrid materials as heterogeneous catalysts for the synthesis of N,N-dimethylformamide from supercritical carbon dioxide

Hybrid materials derived from group VIII metal–chloro complexes of the type MCl2X2(M = Pt, Pd), MClX3(M = Rh, Ir) and especially RuCl2X3[X = Ph2P(CH2)2Si(OEt)3, Me2P(CH2)2Si(OEt)3] by cocondensation with Si(OEt)4via a sol–gel process are highly active heterogeneous catalysts for the synthesis of N,N-dimethylformamide (dmf) from CO2, H2 and dimethylamine under supercritical conditions, affording turnover numbers up to 110 800 at 100% selectivity.