Zirconium and Hafnium Complexes of Enantiopure Iminophosphonamides

Abstract This article reports the design, synthesis, and characterization of four novel metal complexes of zirconium and hafnium stabilized by two enantiopure iminophosphonamide ligands. Enantiopure iminophosphonamines ( R )‐HPEPIA [( R )‐PEPIA = P, P‐diphenyl‐N, N’‐bis(( R )‐1‐ phenylethyl)phosphinimidic amide] and ( R )‐HPE Dipp PIA [( R )‐PE Dipp PIA = P, Pdiphenyl‐N‐(( R )‐1‐phenylethyl), N’‐(2’,6’‐diisopropylaniline) phosphinimidic amide] were reacted with M(NMe 2 ) 4 (M=Zr, Hf) in equimolar ratio to produce metal complexes [{( R )‐PEPIA}M(NMe 2 ) 3 ] (M=Zr ( 1 ), Hf ( 2 )) and [{( R )‐PE Dipp PIA}M(NMe 2 ) 3 ] (M=Zr ( 3 ), Hf ( 4 )), respectively. All these metal complexes were characterized by various analytical and spectroscopic techniques such as multinuclear NMR spectroscopy, elemental analysis, and FTIR spectroscopy; the structure elucidation was done by single crystal X‐ray diffraction technique. Moreover, the catalytic efficiency of the complexes was investigated towards hydroboration and intramolecular hydroamination reactions.