Atypical and Asymmetric 1,3-P,N Ligands : Synthesis, Coordination and Catalytic Performance of Cycloiminophosphanes

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Rong , M K , Holtrop , F , Bobylev , E O , Nieger , M , Ehlers , A W , Slootweg , J C & Lammertsma , K 2021 , ' Atypical and Asymmetric 1,3-P,N Ligands : Synthesis, Coordination and Catalytic Performance of Cycloiminophosphanes ' , Chemistry: A European Journal , vol. 27 , no. 56 , pp. 14007-14016 . https://doi.org/10.1002/chem.202101921

Title: Atypical and Asymmetric 1,3-P,N Ligands : Synthesis, Coordination and Catalytic Performance of Cycloiminophosphanes
Author: Rong, Mark K.; Holtrop, Flip; Bobylev, Eduard O.; Nieger, Martin; Ehlers, Andreas W.; Slootweg, J. Chris; Lammertsma, Koop
Contributor: University of Helsinki, Department of Chemistry
Date: 2021-10-07
Language: eng
Number of pages: 10
Belongs to series: Chemistry: A European Journal
ISSN: 0947-6539
URI: http://hdl.handle.net/10138/335383
Abstract: Novel seven-membered cyclic imine-based 1,3-P,N ligands were obtained by capturing a Beckmann nitrilium ion intermediate generated in situ from cyclohexanone with benzotriazole, and then displacing it by a secondary phosphane under triflic acid promotion. These "cycloiminophosphanes" possess flexible non-isomerizable tetrahydroazepine rings with a high basicity; this sets them apart from previously reported iminophophanes. The donor strength of the ligands was investigated by using their P-kappa(1)- and P,N-kappa(2)-tungsten(0) carbonyl complexes, by determining the IR frequency of the trans-CO ligands. Complexes with [RhCp*Cl-2](2) demonstrated the hemilability of the ligands, giving a dynamic equilibrium of kappa(1) and kappa(2) species; treatment with AgOTf gives full conversion to the kappa(2) complex. The potential for catalysis was shown in the Ru-II-catalyzed, solvent-free hydration of benzonitrile and the Ru-II- and Ir-I-catalyzed transfer hydrogenation of cyclohexanone in isopropanol. Finally, to enable access to asymmetric catalysts, chiral cycloiminophosphanes were prepared from l-menthone, as well as their P,N-kappa(2)-Rh-III and a P-kappa(1)-Ru-II complexes.
Subject: cooperative effects
coordination modes
homogeneous catalysis
ligand design
N
P ligands
MOLECULAR-ORBITAL METHODS
GAUSSIAN-TYPE BASIS
ONE-POT SYNTHESIS
BECKMANN REARRANGEMENT
NITRILIUM IONS
BASIS-SETS
N-IMIDOYLBENZOTRIAZOLES
NEUTRON-DIFFRACTION
3RD-ROW ATOMS
BOND LENGTHS
116 Chemical sciences
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