A MODIFIED WATER-GAS SHIFT REACTION - THE DECOMPOSITION OF ALKYL FORMATE IN THE PRESENCE OF WATER USING A RUTHENIUM CARBONYL

Alkyl formates in the presence of water were rapidly decomposed to H2, CO2 and the corresponding alcohols using Ru3(CO)12 and KOAc as catalyst. Based on the hydrogen gas produced, a turnover rate as fast as 8446/h for ethyl formate at 140-degrees-C was observed. The catalyst system was also active for the decomposition of other alkyl formates. The rate of decomposition increased both with increasing amount of KOAc and with decreasing number of carbon atom in the alkyl group of the formate. In addition to Ru3(CO)12, several other transition metal complexes RuCl3, RuCl2(PPh3)3, Os3(CO)12, H2Os3(CO)10, RhCl3, and RhCl(PPh3)3, were active in the catalytic decomposition of alkyl formates, although their activities varied greatly. The Ru3(CO)12-KOAc system also catalyzed the reduction of nitrobenzene by HCOOEt-H2O to aniline in EtOH and to a mixture of N-phenylformamide and N-methyl-N-phenylformamide in HCOOEt. Under coditions the same as for the hydrogenation of nitrobenzene, ethylene styrene and cyclohexenone were reduced to the corresponding alkanes, whereas 1-hexene and 1-octene were isomerized to the corresponding 2-alkene products.