Reaction of TiF4 and LiORf (Rf = C(CF3)2Ph) in the donor solvent-THF lead to the isolation of the heterometallic lithium–titanium complex (THF)2Li(μ-F)2Ti(ORf)2(μ-F)2Ti(ORf)2(μ-F)2Li(THF)2 (1) and Ti(ORf)4 alkoxide (2). Interaction of TiF4 and LiORf in the non-coordinating and low polar toluene yielded only Ti(ORf)4 (2). Compounds 1 and 2 were characterized by X-ray single-crystal analysis, IR, NMR and mass spectrometry. Compound 1 is a centrosymmetric fluorine bridged dimer and contains the Li(μ-F)2Ti(μ-F)2Ti(μ-F)2Li cage. Complex 2 containing four bulky ligands is monomeric. NMR evidence is presented that the TiF4 and LiORf in THF solution gave lithium–titanium heterometallic complexes containing Li–(μ-F)–Ti and the Ti–(μ-F)–Ti bonds.
