UC Santa Barbara

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 qualitatively the inverse of that of solvent acceptor properties. No intermediates were observed in the reactions. For Pco > 0.1 atm, the rates appeared nearly CO independent although systematic small rate increases were observed at lower PCO. It is suggested that the reaction with Cl− may involve competitive nucleophilic attack at both metal and carbonyl centers. © 1993, American Chemical Society. All rights reserved.