Titanium complexes with unsymmetrically substituted imidazolin-2-iminato ligands

Abstract

The reaction of the unsymmetrical N-heterocyclic carbenes 1-(2,4,6-trimethylphenyl)-3-(adamantyl)imidazolin-2-ylidene (IAdMes, 1a) and 1-(2,6-diisopropylphenyl)-3-(adamantyl)imidazolin-2-ylidene (IAdDipp, 1b) with trimethylsilyl azide furnished the 2-(trimethylsilylimino)imidazolines 2a (Im^AdMesNSiMe₃) and 2b (Im^AdDippNSiMe₃). Desilylation by stirring in methanol gave the corresponding imidazolin-2-imines 3a (Im^AdMesNH) and 3b (Im^AdDippNH). 2a and 2b were treated with [TiCl₄(THF)₂] (THF = tetrahydrofuran) and [CpTiCl₃] (Cp = η⁵-C₅H₅) to form the mono- and bis(imidazolin-2-iminato) titanium(IV) complexes [(Im^AdRN)TiCl₃] (4, R = Mes, Dipp), [Cp(Im^AdRN)TiCl₂] (5, R = Mes, Dipp), and [(Im^AdRN)₂TiCl₂] (6, R = Mes, Dipp). The crystal structures of all compounds except 2b were determined by X-ray diffraction analysis.