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

^*Corresponding author for this work

Research output: Contribution to Journal › Article › Academic › peer-review

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

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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",

year = "2017",

month = mar,

day = "13",

doi = "10.1021/acs.organomet.7b00057",

language = "English",

volume = "36",

pages = "1079--1090",

journal = "Organometallics",

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T1 - Iminophosphanes

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

Abstract

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CCDC 1487762: Experimental Crystal Structure Determination

CCDC 1487761: Experimental Crystal Structure Determination

CCDC 1487763: Experimental Crystal Structure Determination

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

Abstract

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CCDC 1487762: Experimental Crystal Structure Determination

CCDC 1487761: Experimental Crystal Structure Determination

CCDC 1487763: Experimental Crystal Structure Determination

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