Homogeneous decarbonylation of ethyl formate at rhodium. Evidence for the formation of a cis-hydride(ethoxycarbonyl) intermediate through C-H bond cleavage

Article abstract of DOI:10.1016/0022-328X(88)80349-8

The 16-electron fragment <(NP3)Rh>⁺ inserts into the sp² C-H bond of ethyl formate to give the octahedral complex cation <(NP3)Rh(H)(CO2Et)>⁺ which can be isolated in the solid state as SO3CF3^- salt.Thermal decomposition of the cis-hydride(ethoxycarbonyl) complex in benzene gives EtOH and the carbonyl <(NP3)RhCO>(SO3CF3) (NP3 = N(CH2CH2PPh2)3).