Triphenyllead Hydroperoxide: A 1D Coordination Peroxo Polymer, Single-Crystal-to-Single-Crystal Disproportionation to...

The synthesis, transformation, and application in catalysis of triphenyllead hydroperoxide, the first dioxygen lead complex, are described. Triphenyllead hydroperoxide is characterized by ²⁰⁷Pb nuclear magnetic resonance (NMR), Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, and single-crystal X-ray diffraction, revealing the first one-dimensional (1D) coordination peroxo polymer. Photolytic isomorphous transformation of Ph₃PbOOH yields a mixed hydroxo/superoxo crystalline structure, the first nonalkali superoxo crystalline metal salt, which is stable up to 100 °C. Upon further photolysis, another isomorphous transformation of the superoxide to hydroxide is observed. These are the first single-crystal-to-single-crystal hydroperoxide-to-superoxide and then to hydroxide transformations reported to date. Photolysis of triphenyllead hydroperoxide yields two forms of superoxide-doped crystalline structures that are distinguished by widely different characteristic relaxation times. The use of Ph₃PbOOH as an easy-to-handle solid two-electron oxidant for the highly enantioselective epoxidation of olefins is described.