Titanium complexes with two dioxo bridges between the Cp and the metal can be synthesized by the reaction of [Ti{η 5 -C 5 H 3 -1,3-(SiMe 2 Cl) 2 }Cl 3 ] with different diols. Some of these complexes present a dynamic inversion process affording two diastereomers, A and B, which have been studied by X-ray diffraction and NMR techniques. The X-ray diffraction studies of [Ti{η 5 -C 5 H 3 -1,3-[SiMe 2 (κ 1 -1,2-O 2 C 6 H 4 )] 2 }X] X= Cl (2A), Me (4A), and Bn (5) complexes permit their absolute configuration to be assigned, and an epimerization mechanism has been supported by experimental evidence. Moreover, averaged activation energies (ΔH ⧧ , ΔG ⧧ ) and entropies (ΔS ⧧ ) for both the forward and reverse reactions were calculated from the Eyring−Polanyi equation from the NMR EXSY experiments; these are in agreement with the experimental evidence. Article pubs.acs.org/Organometallics

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