Molecular structures of a series of substituted bis(η-cyclopentadienyl)titanium dihalides CpTiX [X = F, Cl, Br and I; R = CHPh, CH(p-Tol) and adamantyl].

Metallocene dihalides and derivatives thereof are of great interest as precursors for catalysts in polymerization reactions, as antitumor agents and, due to their increased stability, as suitable starting materials in salt metathesis reactions and the generation of metallocene fragments. We report the synthesis and structural characterization of a series of eleven substituted bis(η-cyclopentadienyl)titanium dihalides, namely bis[η-1-(diphenylmethyl)cyclopentadienyl]difluoridotitanium(IV), [Ti(CH)F], bis{η-1-[bis(4-methylphenyl)methyl]cyclopentadienyl}difluoridotitanium(IV), [Ti(CH)F], and bis{η-1-[bis(adamantan-2-yl)methyl]cyclopentadienyl}difluoridotitanium(IV), [Ti(CH)F], together with the bromide and iodide analogues, and the chloride analogues of the diphenylmethyl and adamantyl complexes. These eleven complexes were prepared by the reaction of the corresponding bis(η:η-pentafulvene)titanium complexes with different hydrogen halides (Cl, Br and I).

Efficient access to titanaaziridines by C-H activation of N-methylanilines at ambient temperature.

Titanaaziridines or η(2)-imine titanium complexes are considered key intermediates of the titanium-catalyzed hydroaminoalkylation of alkenes. Herein, we present an efficient synthetic route to this class of compounds, starting from N-methylanilines and a bis(η(5):η(1)-pentafulvene)titanium complex. Consecutive reactions on the η(2)-methyleneaniline complexes, characterized for the first time, prove a high chemical versatility.