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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‐κ 1 ‐ and P,N‐κ 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 κ 1  and κ 2  species; treatment with AgOTf gives full conversion to the κ 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‐κ 2 ‐Rh III  and a P‐κ 1 ‐Ru II  complexes.

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