Abstract
The PNNP ligand (R,R)‐{PPh2(2‐C6H4)CH=N(pyrrolidine‐NBn)‐}2 2 was prepared by condensation between 2‐diphenylphosphino benzaldehyde and the pyrrolidine‐substituted diamine 1. Reduction with NaBH4 in MeOH afforded (R,R)‐{PPh2(2‐C6H4)CH–NH(pyrrolidine‐NBn)‐}2 3. The corresponding iron(II) complexes [FeCl2(2)] (4), [Fe(CH3CN)2(2)](BF4)2 (5) and [Fe(CH3CN)2(2)](PF6)2 (6) were synthesized and fully characterized by NMR, ESI‐HRMS, and EA. DFT calculations for complexes [FeCl2(2)] (4) and [Fe(CH3CN)2(2)](BF4)2 (5) were carried out in order to investigate the stability of related structures. The PNNP ligands 2 and 3 in combination with Fe3(CO)12 as iron source were tested as catalysts in the asymmetric transfer hydrogenation of a variety of ketones with conversions higher than 95 % and enantioselectivities up to 97 %.
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