A survey of titanium fluoride complexes, their preparation, reactivity, and applications

• We systematized reactions utilized for the preparation of titanium fluoride complexes.
• We reviewed statement and reactivity of TiF4 in the donor solvents.
• We modeled the relative basicity of ligands in the titanium fluoride complexes.
• We surveyed the reactivity of titanium fluoride complexes.
• Titanium fluoride complexes have numerous applications in the organic synthesis.

A significant amount of information regarding the synthesis, reactivity, and catalytic activity of titanium fluoride complexes is available in the literature. However, the reports are mostly nonsystematic and spread over a large number of specific journals. An attempt is made to collect and organize all available information. Emphasis is given on work published after 1990 with links to the previous reviews, but earlier work is also included if no systematic report was done before.Published synthetic methods to access titanium fluoride complexes are covered in the present review, as well as the properties and reactivity of titanium fluoride complexes. In particular, the behavior of TiF4 in non-aqueous solvents, as well as the interaction of TiF4 with neutral and charged ligands in non-aqueous solvents is reviewed. All published tetrafluoride complexes TiF4L2 (L – neutral ligand) are presented. Mixed chloro and fluoro titanium complexes supported by neutral ligands, their preparation, and isomerism are surveyed. DFT calculations were performed to estimate the relative basicities of molecular ligands in titanium fluoride complexes as well as the relative stability of fluoride bridged titanium complexes.The reactivity of heterometallic titanium–alkali metal, titanium–alkaline earth metal fluoride complexes, the interaction of titanium fluoride complexes with silicon substrates, and the reactivity of titanium complexes toward organofluorine compounds are presented later in the review.Titanium fluoride complexes have found numerous applications in organic synthesis, and in many cases, the fluoride complex shows better performance than do complexes supported by other types of ligands. Organotitanium fluoride complexes show antitumor activity, and their values of cytotoxicity are comparable to that of the “gold standard” cisplatin.

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