Two 18ē TiIVη5‐Cp‐tris(sec‐amido)‐type complexes derived from 1H‐imidazol‐2‐yl side‐chain functionalized cyclopentadienes

Achiral {2‐2‐(η⁵‐cyclopentadienyl)‐2‐methylpropyl]‐1H‐imidazolyl‐κN¹}bis(N,N‐diethylamido‐κN)titanium(IV), Ti(C₄H₁₀N)₂(C₁₂H₁₄N₂)], (I), and closely related racemic (SR)‐{2‐(η⁵‐cyclopentadienyl)(phenyl)methyl]‐1H‐imidazolyl‐κN¹}bis(N,N‐diethylamido‐κN)titanium(IV), Ti(C₄H₁₀N)₂(C₁₅H₁₂N₂)], (II), have been prepared by direct reactions of Ti(NEt₂)₄ and the corresponding 1H‐imidazol‐2‐yl side‐chain functionalized cyclopentadienes. In compound (II), there are two crystallographically independent molecules of very similar geometries connected by a noncrystallographic pseudosymmetry operation akin to a 2₁ screw axis. All Ti‐ligating N atoms in both (I) and (II) are in planar environments, which is indicative of an additional N→Ti pπ–dπ donation. This fact and the 18ē nature of both (I) and (II) are additionally supported by quantum chemical single‐point density functional theory (DFT) computations.