Electrophilic Phosphonium Cation-Mediated Phosphane Oxide Reduction Using Oxalyl Chloride and Hydrogen
Arne J. Stepen
Department of Chemistry, University of Paderborn, Warburger Strasse 100, 33098 Paderborn, Germany
Department of Chemistry, University of Toronto, 80 St. George St, Toronto, Ontario, M5S3H6 Canada
Search for more papers by this authorMarkus Bursch
Mulliken Center for Theoretical Chemistry, University of Bonn, Beringstr. 4, 53115 Bonn, Germany
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Prof. Dr. Stefan Grimme
Mulliken Center for Theoretical Chemistry, University of Bonn, Beringstr. 4, 53115 Bonn, Germany
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Prof. Dr. Douglas W. Stephan
Department of Chemistry, University of Toronto, 80 St. George St, Toronto, Ontario, M5S3H6 Canada
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Prof. Dr. Jan Paradies
Department of Chemistry, University of Paderborn, Warburger Strasse 100, 33098 Paderborn, Germany
Search for more papers by this authorArne J. Stepen
Department of Chemistry, University of Paderborn, Warburger Strasse 100, 33098 Paderborn, Germany
Department of Chemistry, University of Toronto, 80 St. George St, Toronto, Ontario, M5S3H6 Canada
Search for more papers by this authorMarkus Bursch
Mulliken Center for Theoretical Chemistry, University of Bonn, Beringstr. 4, 53115 Bonn, Germany
Search for more papers by this authorCorresponding Author
Prof. Dr. Stefan Grimme
Mulliken Center for Theoretical Chemistry, University of Bonn, Beringstr. 4, 53115 Bonn, Germany
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Prof. Dr. Douglas W. Stephan
Department of Chemistry, University of Toronto, 80 St. George St, Toronto, Ontario, M5S3H6 Canada
Search for more papers by this authorCorresponding Author
Prof. Dr. Jan Paradies
Department of Chemistry, University of Paderborn, Warburger Strasse 100, 33098 Paderborn, Germany
Search for more papers by this authorGraphical Abstract
The metal-free reduction of phosphane oxides with H2 using oxalyl chloride as activating agent was achieved. H2 is activated by the in situ formed electrophilic phosphonium cation and phosphane oxide. The reaction is also catalyzed by B(2,6-F2C6H3)3 and 2,6-lutidine or phosphane oxide as Lewis base.
Abstract
The metal-free reduction of phosphane oxides with molecular hydrogen (H2) using oxalyl chloride as activating agent was achieved. Quantum-mechanical investigations support the heterolytic splitting of H2 by the in situ formed electrophilic phosphonium cation (EPC) and phosphane oxide and subsequent barrierless conversion to the phosphane and HCl. The reaction can also be catalyzed by the frustrated Lewis pair (FLP) consisting of B(2,6-F2C6H3)3 and 2,6-lutidine or phosphane oxide as Lewis base. This novel reduction was demonstrated for triaryl and diaryl phosphane oxides providing access to phosphanes in good to excellent yields (51–93 %).
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