Titanium complexes with unsymmetrically substituted imidazolin-2-iminato ligands

Marvin Koneczny; Arife Büsra Erol; Marc Mauduit; Moris S Eisen; Matthias Tamm

doi:10.1039/d2dt01740g

Titanium complexes with unsymmetrically substituted imidazolin-2-iminato ligands

Dalton Trans. 2022 Aug 2;51(30):11448-11456. doi: 10.1039/d2dt01740g.

Authors

Marvin Koneczny¹, Arife Büsra Erol¹, Marc Mauduit², Moris S Eisen³, Matthias Tamm¹

Affiliations

¹ Institut für Anorganische und Analytische Chemie, Technische Universität Braunschweig, Hagenring 30, 38106 Brauschweig, Germany. m.tamm@tu-bs.de.
² Univ Rennes, Ecole Nationale Supérieure de Chimie de Rennes, CNRS, ISCR-UMR 6226, F-35000 Rennes, France.
³ Schulich Faculty of Chemistry, Technion - Israel Institute of Technology, Technion City, 32000 Haifa, Israel.

PMID: 35822511
DOI: 10.1039/d2dt01740g

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.