A Kinetic Investigation of the Insertion of Ketones into the Dioxygen Adduct Pt(PPh3)2O2

Article abstract of DOI:10.1021/ja00531a014

The kinetics of the insertion reaction A have been studied with different ketones in different solvents.The experimental rate equation is in agreement with a dual pathway reaction mechanism.The major pathway involves precoordination of the ketone to the vacant axial coordination site of platinum followed by insertion.The minor pathway requires a prior activation of the dioxygen moiety.The nature of the transition states and the activated form of the dioxygen complex are discussed by means of an analysis of the activation paramaters and solvent effects.