Felicia L. Taw, A. Clark, A. Mueller
Jan 27, 2012
Citations
1
Influential Citations
37
Citations
Journal
Organometallics
Abstract
Trifluoromethyltrimethylsilane, (CH3)3SiCF3, in the presence of CsF serves as an excellent CF3 group-transfer reagent, and reaction with Cp2TiF2 in THF gives the titanocene trifluoromethyl fluoride complex Cp2Ti(CF3)(F) (1; Cp = C5H5) in 60% isolated yield. Reaction of complex 1 with the trimethylsilyl reagents, (CH3)3SiX (X = OTf = OSO2CF3, Cl, Br, I, N3, and OSO2Ph), in a tetrahydrofuran or toluene solution affords the corresponding Ti–CF3 derivatives Cp2Ti(CF3)(X) (X = OTf (2), Cl (12), Br (13), I (14), N3 (15), and OSO2Ph (16)) in good isolated yields of 67–84%. These compounds have been characterized by a combination of reactivity studies, IR and 1H/13C{1H}/19F NMR spectroscopies, and single-crystal X-ray diffraction. The Ti–CF3 linkage in these complexes is remarkably robust, and although the α-C–F bonds are elongated, there is no evidence of an α-fluoride (Ti···F–CF2) between the electrophilic Ti(IV) metal center and any of the C–F bonds in the trifluoromethyl group in the solid-state or in solutio...