Catalytic transfer hydrogenation by a trivalent phosphorus compound: phosphorus-ligand cooperation pathway or P(III) /P(V) redox pathway?
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.
Journal
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- Angewandte Chemie
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Angewandte Chemie 53 (18), 4633-4637, 2014-04-25
wiley
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Keywords
Details
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- CRID
- 1050564285766987776
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- NII Article ID
- 120005646481
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- ISSN
- 15213773
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- HANDLE
- 2433/199584
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- Text Lang
- en
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- Article Type
- journal article
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- Data Source
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- IRDB
- CiNii Articles