Neue titanocen-derivate mit aminothiophenolat-liganden

Abstract

Titanocene dichloride (Cp 2TiCl 2; Cp = η 5-C 5H 5) reacts with the alkali aminothiophenolates NaSC 6H 4NH 2- o or LiSC 6H 4NH 2- p in tetrahydrofuran or benzene at room temperature. According to the applied stoichiometry, one or both of the chloride ligands are substituted, and the mono- or bis(aminothiophenolato) complexes Cp 2TiCl(SC 6H 4NH 2- o) (Ia), Cp 2TiCl(SC 6H 4NH 2- p) (Ib), Cp 2Ti(SC 6H 4NH 2 - o) 2 (IIa), or Cp 2Ti(SC 6H 4NH 2- p) 2 (IIb) are formed. Analogously, from Cp 2Ti(Cl)CH 3 Cp 2TiCH 3(SC 6H 4NH 2- o) (IIIa) or Cp 2TiCH 3(SC 6H 4NH 2- p) (IIIb) are obtained. IIb, which was isolated as a mixture with Ib, can be prepared in a pure state from Cp 2TiCl 2 and p-aminothiophenol in ether with trithylamine as supporting base. All substances were investigated by IR, 1H NMR and mass spectrometry. Fragmentation diagrams, based on the detection of metastable decays in the mass spectrometer, were established.