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Catalytic Epoxidations with Peroxides: Molybdenum Trioxide Species as the Origin of Allylic Byproducts
Author(s) -
Neuenschwander Ulrich,
Meier Emanuel,
Hermans Ive
Publication year - 2012
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201200470
Subject(s) - allylic rearrangement , molybdenum , chemistry , molybdenum trioxide , catalysis , reagent , peroxide , radical , selectivity , photochemistry , molybdenum oxide , inorganic chemistry , organic chemistry
Molybdenum(VI)peroxide species, formed in the reaction of Mo VI complexes with peroxides, are able to epoxidize >CC< double bonds heterolytically. In this study, theoretical and experimental evidence is provided for a kinetically competing reaction reaction of such molybdenum(VI)peroxide species with additional peroxide reagent, leading to molybdenum(VI)trioxide species, which easily decompose into radicals. Under epoxidation conditions, those radicals will reduce the selectivity, due to the formation of allylic byproducts. The involved reaction pathways are characterized by DFT calculations, providing kinetic parameters that are in good agreement with the experimental observations.