Metal Imido Complexes (M=Ti, W) Containing 2‐(Dimethylaminomethyl)pyrrole: Synthesis and the Crystal Structures of Bu^tN=TiCIPy₂[2‐Me₂NCH₂(C₄H₃N)] and PhN=WCl₃[2‐Me₂NCH₂(C₄H₃N)]

Abstract

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.

Synthesis, Structures and Characterization of the Calcium Pyrrolates [Ca{(2‐(dimethylaminomethyl)pyrrolyl}2 donorn] (donor = THF and pyridine, n = 2; DME and TMEDA, n = 1) as Potential Precursors for Solid‐State Applications

“…In fact, welcharacterized main group derivatives are limited to aluminum, [13] gallium and indium [14] in addition to some recently published mixed magnesium cyclopentadienide/amido derivatives. [15] Other metal complexes bearing DMAMP-type ligands include titanium, [16] tungsten, [16] zirconium, [17Ϫ19] vanadium, [19] thallium, [20] chromium, [19] molybdenum, [21] cobalt [19] and nickel. [19] Pyrrolylcalcium and -strontium derivatives with two tertbutyl substituents have been reported.…”