Premium
Catalytic Transfer Hydrogenation by a Trivalent Phosphorus Compound: Phosphorus‐Ligand Cooperation Pathway or P III /P V Redox Pathway?
Author(s) -
Zeng Guixiang,
Maeda Satoshi,
Taketsugu Tetsuya,
Sakaki Shigeyoshi
Publication year - 2014
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201311104
Subject(s) - phosphorus , redox , chemistry , catalysis , ligand (biochemistry) , inorganic chemistry , organic chemistry , receptor , biochemistry
Main‐group‐element catalysts are a desirable alternative to transition‐metal catalysts because of natural abundance and cost. However, the examples are very limited. Catalytic cycles involving a redox process and E‐ligand cooperation (E=main‐group element), which are often found in catalytic cycles of transition‐metal catalysts, have not been reported. Herein theoretical investigations of a catalytic hydrogenation of azobenzene with ammonia–borane using a trivalent phosphorus compound, which was experimentally proposed to occur through P III /P V redox processes via an unusual pentavalent dihydridophosphorane, were performed. DFT and ONIOM(CCSD(T):MP2) calculations disclosed that this catalytic reaction occurs through a P‐O cooperation mechanism, which resembles the metal‐ligand cooperation mechanism of transition‐metal catalysts.