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Kinetics and mechanism of self‐decomposition/reduction of oxo bis (peroxo) pyridine chromium(VI) in nonaqueous solvents
Author(s) -
Toofan Jahansooz,
Vessal Behnam
Publication year - 2021
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.21520
Subject(s) - chemistry , chromium , kinetics , pyridine , decomposition , reaction mechanism , reaction rate constant , inorganic chemistry , solvent , photochemistry , organic chemistry , catalysis , physics , quantum mechanics
Kinetics of oxidation of phenylmethanol, as a model by the oxo bis (peroxo) pyridine chromium(VI), OPPC, has been studied in different nonaqueous solvents. Decomposition of oxidant in solvents is studied and explained. The probable mechanism of the reaction is expounded and is related to the kinetics data. Furthermore, the data show a hydride abstraction by η2‐peroxo, forming a terminal oxo plus hydroxo ligand. The effects of solvent dielectric constant on the reaction rates are then considered. A formal potential (0.87 V) decomposition of OPPC on the Pt electrode is measured, which is accompanied by a one‐electron transition in determining the reaction. In addition, thermodynamic parameters are calculated and discussed based upon the proposed reaction mechanism.