Ferrocene--derived ligands and their reactions with titanium, organotitanium, zirconium and organozirconium compounds

摘要

Reactions of 1-formylferrocene-4-methoxybenzoylhydrazone (HFfmbh) and 1-acetylferrocene-4-methoxybenzoylhydrazone (HAfmbh) with TiCl_4(thf)_2, ZrCl_4(thf)_2 (thf = tetrahydrofuran), (#pi#-C_5H_5)TiCl_3, (#pi#-C_5H_5)TiCl_3(OMe), TiCl_2(OMe)_2 and (#pi#-C_5H_5)_2ZrCl_3 yield complexes of the types (Lig)_2TiCl_2, (Lig)_2ZrCl_2(thf), (#pi#-C_5H_5)Ti(Lig)_2X, Ti(Lig)_2X_2 and (#pi#-C_5H_5)Zr(Lig)_2Cl (where Hlig = HFfmbh and Hafmbh; X = Cl and OMe). Reaction of (Ffmbh)_2TiCl_2 with LiMe in benzene yields dimethyl derivative (Ffmbh)_2TiMe_2, while that of (Ffmbh)_2TiCl_2 with PhMgBr in the affords organotitanium(III) species (Ffmbh)_2Ti(Ph)thf. On the other hand, reactions of (#pi#-C_5H_5_Ti(Ffmbhh)_2Cl, also synthesized in this study, with MeSH, Me_3Si(Nme_2), Me_3Si(N_3) and Me_3NiC(ident to)C-Ph afford (#pi#-C_5H_5)Ti(Ffmbh)_2L~1 (where L~1 = SMe, Nme_2, N_3 and =C(ident to)C-Ph). Both the ligands function in a monobasic bidentate fashion in the complexes and the deprotonated enolic form of the ligand is involved in the coordination to the metal.