Insertion of Dioxygen into a Platinum−Hydride Bond to Form a Novel Dialkylhydroperoxo Pt(IV) Complex

Abstract

The selective catalytic oxidation of alkanes using inexpensive and environmentally friendly oxidants is of immense interest to the chemical community and of great potential benefit to the world economy and ecology. Since the earliest reports that the oxidative addition of alkane C-H bonds to transition metal species can occur with high selectivities, substantial research effort has focused on the functionalization of the metal alkyl hydride products. The authors report that Pt(IV) dialkyl hydride complex reacts cleanly with dioxygen to produce a dialkyl Pt(IV) hydroperoxide species. Of potential relevance to the development of alkane oxidation systems is that the Pt(IV) dialkyl hydride reactant is analogous to compounds formed by intermolecular oxidative addition of alkane C-H bonds to Pt(II). The novel Pt(IV) product has been crystallographically characterized and displays an {eta}-hydroperoxide linkage.