Lorber Christian, Choukroun Robert, Vendier Laure
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.
Inorg Chem. 2007 Apr 16;46(8):3192-202. doi: 10.1021/ic062404j. Epub 2007 Mar 16.
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.
对甲苯磺酰胺（p - TsNH₂）成功地用作亚胺配体前体，用于合成对空气和湿气高度敏感的钛（IV）和钒（IV）配合物。M（NMe₂）₄（M = Ti，V）与TsNH₂在甲苯中反应得到二聚体配合物[M（μ - NTs）（NMe₂）₂]₂（M = Ti（1），V（2））。相比之下，在二氯甲烷中进行的反应通过溶剂活化生成了[Ti[μ - N，O - NTs]Cl（NMe₂）（NHMe₂）₂]₂（3）和[Ti[μ - N，O - NTs]Cl₂（NHMe₂）₂]ₙ（4）。在过量三甲基氯硅烷存在下进行的M（NMe₂）₄/TsNH₂相同反应生成了[V（=NTs）Cl₂（NHMe₂）₂]（5）和[（Me₂HN）Cl₂Ti（μ₂ - N - NTs - κ²N，O）₂TiCl₂（NHMe₂）₂]（6）。另外，化合物6也可由TiCl₂（NMe₂）₂和TsNH₂制备。1与三甲基氯硅烷反应得到酰胺配合物[Ti[μ - N，O'-N（SiMe₃）Ts - κ³N，O，O']Cl₂（NMe₂）]₂（7），其中对甲苯磺酰亚胺键已被硅烷化。化合物l - 6代表了钛和钒的磺酰亚胺配合物的首例。
