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Title: Catalytic transfer hydrogenation by a trivalent phosphorus compound: phosphorus-ligand cooperation pathway or P(III) /P(V) redox pathway?
Authors: Zeng, Guixiang
Maeda, Satoshi
Taketsugu, Tetsuya
Sakaki, Shigeyoshi
Author's alias: 榊, 茂好
Keywords: density functional calculations
hydrogenation
main-group elements
phosphorus
redox chemistry
Issue Date: 25-Apr-2014
Publisher: wiley
Journal title: Angewandte Chemie
Volume: 53
Issue: 18
Start page: 4633
End page: 4637
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.
Rights: This is the peer reviewed version of the following article: Zeng, G., Maeda, S., Taketsugu, T. and Sakaki, S. (2014), Catalytic Transfer Hydrogenation by a Trivalent Phosphorus Compound: Phosphorus-Ligand Cooperation Pathway or PIII/PV Redox Pathway?. Angew. Chem. Int. Ed., 53: 4633–4637, which has been published in final form at http://dx.doi.org/10.1002/anie.201311104. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving.
This is not the published version. Please cite only the published version. この論文は出版社版でありません。引用の際には出版社版をご確認ご利用ください。
URI: http://hdl.handle.net/2433/199584
DOI(Published Version): 10.1002/anie.201311104
PubMed ID: 24668586
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