Insertion and related reactions of bis(η-cyclopentadienyl)dimethyltitanium, η-cyclopentadienyltrimethyltitanium, and trichloro(η-cyclopentadienyl)titanium and other titanium compounds

Abstract

The reaction of [(cp)₂TiMe₂] with cyclohexyl isocyanide (C₆H₁₁NC) yields the complex [(cp)₂TiMe{C(Me):NC₆H₁₁}], which further reacts with iodine to give the complex [(cp)₂Til{C(Me):NC₆H₁₁}]. The reactions of [(cp)TiMe₃] with NO, SO₂, RNC (R = C₆H₁₁ or p-tolyl), MeNCO and PhNCS have been studied and the complexes [(cp)TiMe{ON(Me)NO}₂] and [(cp)TiMe₂(SO₂Me)] have been isolated and characterised. The reactions of [(cp)TiCl₃] and [(cp)TiMe₃] with Lewis bases have been studied and the complexes [(cp)TiCl₃(diars)] and [(cp)TiCl₃(bipy)] isolated [diars =o-phenylenebis(dimethylarsine), bipy = 2,2′-bipyridyl]. The complexes [(cp)₂TiBr(OCH₂CH₂CH:CH₂)] and [(cp)TiMe₂(OCH₂CH₂CH:CH₂)] have been prepared and it has been shown that the olefinic group is not co-ordinated to the titanium atom in either case. Attempts to co-ordinate the olefinic grouping of the ligand Me₂N·CH₂·CH₂·N(Me)·CH₂·CH₂·CH:CH₂ to titanium tetrachloride and titanium trichloride are also described.