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DFT Study of the Molybdenum‐Catalyzed Deoxydehydration of Vicinal Diols
Author(s) -
Lupp Daniel,
Christensen Niels Johan,
Dethlefsen Johannes R.,
Fristrup Peter
Publication year - 2015
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.201405473
Subject(s) - molybdenum , vicinal , catalysis , alkene , diol , chemistry , density functional theory , cleavage (geology) , condensation , sulfoxide , combinatorial chemistry , computational chemistry , organic chemistry , materials science , physics , fracture (geology) , composite material , thermodynamics
The mechanism of the molybdenum‐catalyzed deoxydehydration (DODH) of vicinal diols has been investigated using density functional theory. The proposed catalytic cycle involves condensation of the diol with an Mo VI oxo complex, oxidative cleavage of the diol resulting in an Mo IV complex, and extrusion of the alkene. We have compared the proposed pathway with several alternatives, and the results have been corroborated by comparison with the molybdenum‐catalyzed sulfoxide reduction recently published by Sanz et al. and with experimental observations for the DODH itself. Improved understanding of the mechanism should expedite future optimization of molybdenum‐catalyzed biomass transformations.