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

Publication date

2017-03-13

Authors

Rong, Mark K.
Van Duin, Koen
Van Dijk, Tom
De Pater, Jeroen J.M.
Deelman, Berth Jan
Nieger, Martin
Ehlers, A. W.
Slootweg, J. Chris
Lammertsma, Koop

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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 κ1 and κ2 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.

Keywords

Physical and Theoretical Chemistry, Organic Chemistry, Inorganic Chemistry

Citation

Rong, M K, Van Duin, K, Van Dijk, T, De Pater, J J M, Deelman, B J, Nieger, M, Ehlers, A W, Slootweg, J C & Lammertsma, K 2017, 'Iminophosphanes : Synthesis, Rhodium Complexes, and Ruthenium(II)-Catalyzed Hydration of Nitriles', Organometallics, vol. 36, no. 5, pp. 1079-1090. https://doi.org/10.1021/acs.organomet.7b00057