Nucleophilic activation of carbon monoxide. A kinetics investigation of the reaction of chloride with triruthenium dodecacarbonyl

Kinetics studies of the reaction of the triruthenium cluster Ru[sub 3](CO)[sub 12] with the [open quotes]highly dissociated[close quotes] chloride salt [PPN]Cl to give the Ru[sub 3](CO)[sub 11]Cl[sup [minus]] anion in THF/CH[sub 2]Cl[sub 2] solutions show a rate law first order in [Cl[sup [minus]]] and in [Ru[sub 3](CO)[sub 12]]. Rates are significantly higher in 90/10 than in 80/10 (v/v) THF/CH[sub 2]Cl[sub 2] solutions, and the reactivity order is qualitatively the inverse of that of solvent acceptor properties. No intermediates were observed in the reactions. For P[sub CO] > 0.1 atm, the rates appeared nearly CO independent although systematic small rate increases were observed at lower P[sub CO]. It is suggested that the reaction with Cl[sup [minus]] may involve competitive nucleophilic attack at both metal and carbonyl centers.