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Updated: May 1, 2026
Preparation and Use of Carbonyl-decorated Carbenes in the Activation of White Phosphorus
Published on: October 3, 2014
Catalytic transfer hydrogenation by a trivalent phosphorus compound: phosphorus-ligand cooperation pathway or P(III)
Guixiang Zeng1, Satoshi Maeda, Tetsuya Taketsugu
1Fukui Institute for Fundamental Chemistry, Kyoto University, Takano-Nishihiraki-cho 34-4, Sakyo-ku, Kyoto 606-8103 (Japan).
Abstract:
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.
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