Highly active ruthenium complexes with bidentate phosphine ligands for the solvent-free catalytic synthesis of N,N-dimethylformamide and methyl formate

Complexes of the type [RuCl(2)L(2)] [L = Ph(2)P(CH2)(n)PPh(2) (n = 1-3), Me(2)P(CH2)(2)PMe(2)] are shown to be highly active and selective catalysts for the synthesis of formic acid derivatives from carbon dioxide, hydrogen and dimethylamine or methanol-triethylamine, respectively, without any additional solvent, affording at 373 K with [RuCl2(dppe)(2)] an extremely high turnover frequency (TOF) of 360 000 h(-1) in N,N-dimethylformamide synthesis and a TOF of 830 h(-1) in methyl formate synthesis.