TY - JOUR
T1 - Triphenyllead Hydroperoxide
T2 - A 1D Coordination Peroxo Polymer, Single-Crystal-to-Single-Crystal Disproportionation to a Superoxo/Hydroxo Complex, and Application in Catalysis
AU - Medvedev, Alexander G.
AU - Grishanov, Dmitry A.
AU - Mikhaylov, Alexey A.
AU - Churakov, Andrei V.
AU - Tripol'Skaya, Tatiana A.
AU - Ottenbacher, Roman V.
AU - Bryliakov, Konstantin P.
AU - Shames, Alexander I.
AU - Lev, Ovadia
AU - Prikhodchenko, Petr V.
N1 - Publisher Copyright:
© 2022 American Chemical Society. All rights reserved.
PY - 2022/5/30
Y1 - 2022/5/30
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=85131269007&partnerID=8YFLogxK
U2 - 10.1021/acs.inorgchem.2c00487
DO - 10.1021/acs.inorgchem.2c00487
M3 - Article
C2 - 35578736
AN - SCOPUS:85131269007
SN - 0020-1669
VL - 61
SP - 8193
EP - 8205
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 21
ER -