Iminophosphanes: Synthesis, Rhodium Complexes, and Ruthenium(II)-Catalyzed Hydration of Nitriles.
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 κ1and κ2complexes 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.
Department of Chemistry and Pharmaceutical Sciences, Vrije Universiteit Amsterdam , De Boelelaan 1083, 1081 HV Amsterdam, The Netherlands.
Mark K
MK
Rong
Department of Chemistry and Pharmaceutical Sciences, Vrije Universiteit Amsterdam , De Boelelaan 1083, 1081 HV Amsterdam, The Netherlands.
Koen
K
van Duin
Department of Chemistry and Pharmaceutical Sciences, Vrije Universiteit Amsterdam , De Boelelaan 1083, 1081 HV Amsterdam, The Netherlands.
Tom
T
van Dijk
Arkema B.V. , location Vlissingen, P.O. Box 70, 4380 AB Vlissingen, The Netherlands.
Jeroen J M
JJ
de Pater
Arkema B.V. , location Vlissingen, P.O. Box 70, 4380 AB Vlissingen, The Netherlands.
Berth-Jan
BJ
Deelman
Laboratory of Inorganic Chemistry, Department of Chemistry, University of Helsinki , A. I. Virtasen aukio 1, P. O. Box 55, Helsinki, Finland.
Martin
M
Nieger
Department of Chemistry and Pharmaceutical Sciences, Vrije Universiteit Amsterdam, De Boelelaan 1083, 1081 HV Amsterdam, The Netherlands; Department of Chemistry, University of Johannesburg, Oakland Park 2006, South Africa.
A W
AW
Ehlers
Department of Chemistry and Pharmaceutical Sciences, Vrije Universiteit Amsterdam , De Boelelaan 1083, 1081 HV Amsterdam, The Netherlands.
J Chris
JC
Slootweg
Department of Chemistry and Pharmaceutical Sciences, Vrije Universiteit Amsterdam, De Boelelaan 1083, 1081 HV Amsterdam, The Netherlands; Department of Chemistry, University of Johannesburg, Oakland Park 2006, South Africa.
Koop
K
Lammertsma