title: Reaction of p-toluenesulfonylamide and M(NMe2)4 (M = Ti, V): generation of electron-deficient imido complexes of early transition metals.
abstract: p-Toluenesulfonamide (p-TsNH2) was successfully employed as an imido ligand precursor in the synthesis of highly air- and moisture-sensitive titanium(IV) and vanadium(IV) complexes. Reaction of M(NMe2)4 (M = Ti, V) with TsNH2 in toluene afforded [M(micro-NTs)(NMe2)2]2 dimer complexes (M = Ti (1), V (2)). By contrast, the reaction carried out in dichloromethane led to [Ti[micro-N,O-NTs]Cl(NMe2)(NHMe2)2]2 (3) and [Ti[micro-N,O-NTs]Cl2(NHMe2)2]n (4) through solvent activation. The same reaction of M(NMe2)4/TsNH2 conducted in the presence of an excess of trimethylchlorosilane produced [V(=NTs)Cl2(NHMe2)2] (5) and [(Me2HN)Cl2Ti(micro2-N-NTs-kappa2N,O)2TiCl2(NHMe2)2] (6). Alternatively, compound 6 has also been prepared from TiCl2(NMe2)2 and TsNH2. 1 was reacted with trimethylchlorosilane to afford the amide complex [Ti[micro-N,O'-N(SiMe3)Ts-kappa3N,O,O']Cl2(NMe2)]2 (7) in which the tosylimide bond has been silylated. Compounds 1-6 represents the first examples of sulfonylimido complexes for titanium and vanadium.
authors.affiliation: Laboratoire de Chimie de Coordination, CNRS UPR 8241, lié par convention à l'Université Paul Sabatier, 205 route de Narbonne, 31077 Toulouse Cedex 04, France. lorber@lcc-toulouse.fr
authors.forename: Christian
authors.initials: C
authors.lastname: Lorber
authors.forename: Robert
authors.initials: R
authors.lastname: Choukroun
authors.forename: Laure
authors.initials: L
authors.lastname: Vendier
mesh_terms: D018360:Crystallography, X-Ray; D004583:Electrons; D007094:Imides / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism; D013449:Sulfonamides / Q000737:chemistry*; D014050:Toluene / Q000031:analogs & derivatives* / Q000737:chemistry; D028561:Transition Elements / Q000737:chemistry*; D000096926:Benzenesulfonamides
chemical_list: D007094:Imides; D009942:Organometallic Compounds; D013449:Sulfonamides; D014050:Toluene; D028561:Transition Elements; C025417:4-toluenesulfonamide; D000096926:Benzenesulfonamides