NUCLEOPHILIC ACTIVATION OF CARBON-MONOXIDE - A KINETICS INVESTIGATIONOF THE REACTION OF CHLORIDE WITH TRIRUTHENIUM DODECACARBONYL

Kinetics studies of the reaction of the triruthenium cluster Ru3(CO)12 with the 'highly dissociated'' chloride salt [PPN]Cl to give the Ru3( CO)11Cl- anion in THF/CH2Cl2 solutions show a rate law first order in [Cl-] and in [Ru3(CO)12]. Rates are significantly higher in 90/10 than in 80/10 (v/v) THF/CH2Cl2 solutions, and the reactivity order is qual itatively the inverse of that of solvent acceptor properties. No inter mediates were observed in the reactions. For P(CO) > 0.1 atm, the rate s appeared nearly CO independent although systematic small rate increa ses were observed at lower P(CO). It is suggested that the reaction wi th Cl- may involve competitive nucleophilic attack at both metal and c arbonyl centers.