Reaction of p-toluenesulfonylamide and M(NMe2)4 (M = Ti, V): generation of electron-deficient imido complexes of early transition metals

Inorg Chem. 2007 Apr 16;46(8):3192-202. doi: 10.1021/ic062404j. Epub 2007 Mar 16.

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.

MeSH terms

  • Crystallography, X-Ray
  • Electrons*
  • Imides / chemistry*
  • Models, Molecular
  • Molecular Conformation
  • Organometallic Compounds / chemical synthesis*
  • Organometallic Compounds / chemistry
  • Stereoisomerism
  • Sulfonamides / chemistry*
  • Toluene / analogs & derivatives*
  • Toluene / chemistry
  • Transition Elements / chemistry*

Substances

  • Imides
  • Organometallic Compounds
  • Sulfonamides
  • Transition Elements
  • Toluene
  • 4-toluenesulfonamide