Synthesis and Structure of Titanium Imido Complexes With Bi‐ and Tridentate PN and PNP Ligands

We report the synthesis of alkyl and aryl imido titanium(IV) complexes supported by bi‐ or tridentate PN Mes and PNP ligands (PN Mes = (2‐(diisopropylphosphanyl)‐4‐methylphenyl)( N ‐mesityl)‐anilide, PNP = bis(2‐(diisopropylphosphanyl)‐4‐methylphenyl)anilide) giving access to penta‐coordinate titanium imido complexes. Spectroscopic and structural investigations reveal that in the case of the PNP complexes, no additional solvent donors are coordinated to the titanium center, while with bidentate PN ligands, the coordination sphere of the titanium is filled by an additional pyridine donor. The catalytic potential of these complexes in the intramolecular hydroamination reaction of 2,2‐diphenylpent‐4‐en‐1‐amine is further evaluated, showing the PN complex readily engaging in the cyclization reaction, while its PNP analog exhibits no catalytic activity.