Reactions of ZrCl 4 with 2 or 3 equiv of Li- 2), respectively. Compounds 1 and 2 are characterized by NMR spectroscopy and single-crystal X-ray diffraction. Compound 1 exists as a six-coordinate octahedral structure with the two NMe 2 units taking trans positions, and the seven-coordinate compound 2 shows a chloridecapped octahedral structure in which three bidentate pyrrole ligands form a pseudo-propeller structure with a δλλ form. A polymerization study shows that compounds 1 and 2 exhibit moderate activity toward ethylene, with compound 2 having higher activity.

A titanium imido complex, ButN=TiClPy2[2‐Me2NCH2‐(C4H3N)] 1, was synthesized through metathesis by reacting ButN=TiCl2Py3 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 1at −20°C and the monoclinic crystal shows a distorted octahedral structure with two pyridines taking trans positions. Hydrolysis ButN=TiCl2Py3 with 2,2′‐methylene‐bis(6‐t‐butyl‐4‐methylphenol) (HO∼∼CH2∼∼OH)generates a bis phenoxide titanium complex, (O∼∼CH2∼∼O)TiCl2Py 2, by eliminating one equivalent of ButNH2. Similarly, the reaction of LH with PhN=WCl4(OEt2) in diethyl ether at room temperature generates PhN=WCl3(L) 3, in moderate yield. 3has been characterized by NMR spectroscopies and X‐ray crystallography.