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Iminophosphanes: Synthesis, Rhodium Complexes, and Ruthenium(II)-Catalyzed Hydration of Nitriles.


ABSTRACT: Highly stable iminophosphanes, obtained from alkylating nitriles and reaction of the resulting nitrilium ions with secondary phosphanes, were explored as tunable P-monodentate and 1,3-P,N bidentate ligands in rhodium complexes. X-ray crystal structures are reported for both ?1 and ?2 complexes with the counterion in one of them being an unusual anionic coordination polymer of silver triflate. The iminophosphane-based ruthenium(II)-catalyzed hydration of benzonitrile in 1,2-dimethoxyethane (180 °C, 3 h) and water (100 °C, 24 h) and under solvent free conditions (180 °C, 3 h) results in all cases in the selective formation of benzamide with yields of up to 96%, thereby outperforming by far the reactions in which the common 2-pyridyldiphenylphosphane is used as the 1,3-P,N ligand.

SUBMITTER: Rong MK 

PROVIDER: S-EPMC5350608 | biostudies-literature | 2017 Mar

REPOSITORIES: biostudies-literature

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Iminophosphanes: Synthesis, Rhodium Complexes, and Ruthenium(II)-Catalyzed Hydration of Nitriles.

Rong Mark K MK   van Duin Koen K   van Dijk Tom T   de Pater Jeroen J M JJ   Deelman Berth-Jan BJ   Nieger Martin M   Ehlers A W AW   Slootweg J Chris JC   Lammertsma Koop K  

Organometallics 20170216 5


Highly stable iminophosphanes, obtained from alkylating nitriles and reaction of the resulting nitrilium ions with secondary phosphanes, were explored as tunable P-monodentate and 1,3-P,N bidentate ligands in rhodium complexes. X-ray crystal structures are reported for both κ<sup>1</sup> and κ<sup>2</sup> complexes with the counterion in one of them being an unusual anionic coordination polymer of silver triflate. The iminophosphane-based ruthenium(II)-catalyzed hydration of benzonitrile in 1,2-  ...[more]

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