Aromatic Imines in the Titanocene Coordination Sphere-Titanaaziridine vs 1-Aza-2-titanacyclopent-4-ene Structures

Two independent synthetic routes to eta(2)-imine titanocene complexes were developed. On one hand side, ligand exchange reactions of bis(trimethylsilyl)acetylene by (p-Tolyl)HC-NPh (3) employing the Rosenthal reagent Cp2Ti{eta(2)-C-2(SiMe3)(2)} (1) lead to Cp2Ti{eta(2)-(p-Tolyl)CH-NPh} (5), exhibiting a titanaaziridine structure. On the other hand, the direct reductive complexation of 3 by using Cp2TiCl2 (2) and Mg as reducing agent leads also to 5, one of the rare known titanoceneaziridines without additional ligands. By using the ketimine (p-Tolyl)(2)C-NPh (4) instead of the aldimine 3, an unexpected coordination mode was found by X-ray diffraction, exhibiting an azatitanacyclopent-4-ene structure involving one tolyl fragment. In such a way, via the reductive complexation of 4, employing 2 or Cp*TiCl3 (12), the 1-aza-2-titanacyclopent-4-ene complexes 6 and 13 are formed. Density functional calculations at the M06-2X level identify these new complexes 6 and 13 as 1-aza-2-titanacyclopent-4-enes, in agreement with an analysis based on the experimental structural parameters. A theoretical study of the bonding between the titanocene fragment and the imine ligand reveals that steric factors are more pronounced for titanaaziridines and disfavor their formation compared to azatitanacyclopentenes. This provides a rationalization for the preferred formation of titanoceneaziridines in the case of aldimine ligands and azatitanacyclopentenes when ketimines are applied. Whereas titanoceneaziridine 5 undergoes insertion reactions into the TiC carbon s-bond with aldehydes, ketones, or carbodiimides to the five-membered titanacycles 20 and 21, complex 6 appears to be inert in comparable reactions