SUBSTITUTION REACTIONS OF RU3(CO)12

The kinetics of substitution reactions of Ru3(CO)12 using Group V donor ligands to yield complexes of the type Ru3(CO)9L3 have been studied. By comparison with published Ru3(CO)12/CO exchange experiments, the rate determining step for substitution is thought to be the reversible dissociation of CO, yielding the intermediate Ru3(CO)11. The formation of radical intermediates [Ru(CO)4] or [(CO)4Ru-Ru(CO)4-Ru(CO)4] appears unlikely. No indication of formation of stable complexes Ru3(CO)1, PPh3 or Ru3(CO)10(PPh3)2 during the course of the reaction with PPh3 could be found. © 1969.