Metal Imido Complexes (M=Ti, W) Containing 2‐(Dimethylaminomethyl)pyrrole: Synthesis and the Crystal Structures of Bu t N=TiCIPy 2 [2‐Me 2 NCH 2 (C 4 H 3 N)] and PhN=WCl 3 [2‐Me 2 NCH 2 (C 4 H 3 N)]

A titanium imido complex, Bu t N=TiClPy 2 [2‐Me 2 NCH 2 ‐(C 4 H 3 N)] 1 , was synthesized through metathesis by reacting Bu t N=TiCl 2 Py 3 with lithium 2‐(dimethylaminomethyl) pyrrolate (LLi) in diethyl ether at room temperature. The dark brown red crystals were obtained from a concentrated diethyl ether solution of compound 1 at −20°C and the monoclinic crystal shows a distorted octahedral structure with two pyridines taking trans positions. Hydrolysis Bu t N=TiCl 2 Py 3 with 2,2′‐methylene‐bis(6‐t‐butyl‐4‐methylphenol) (HO∼∼CH 2 ∼∼OH) generates a bis phenoxide titanium complex, (O∼∼CH 2 ∼∼O)TiCl 2 Py 2 , by eliminating one equivalent of Bu t NH 2 . Similarly, the reaction of LH with PhN=WCl 4 (OEt 2 ) in diethyl ether at room temperature generates PhN=WCl 3 (L) 3 , in moderate yield. 3 has been characterized by NMR spectroscopies and X‐ray crystallography.