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

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

doi:10.1021/acs.organomet.7b00057

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

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

Chemical Sciences

Research output: Contribution to journal › Article › peer-review

27 Citations (Scopus)

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.

Original language	English
Pages (from-to)	1079-1090
Number of pages	12
Journal	Organometallics
Volume	36
Issue number	5
DOIs	https://doi.org/10.1021/acs.organomet.7b00057
Publication status	Published - 13 Mar 2017

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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title = "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 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.",

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

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T2 - Synthesis, Rhodium Complexes, and Ruthenium(II)-Catalyzed Hydration of Nitriles

AU - Rong, Mark K.

AU - Van Duin, Koen

AU - Van Dijk, Tom

AU - De Pater, Jeroen J.M.

AU - Deelman, Berth Jan

AU - Nieger, Martin

AU - Ehlers, A. W.

AU - Slootweg, J. Chris

AU - Lammertsma, Koop

PY - 2017/3/13

Y1 - 2017/3/13

N2 - 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.

AB - 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.

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JF - Organometallics

IS - 5

ER -

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

Abstract

ASJC Scopus subject areas

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