AbstractReactions of CH3OCH2CH2OH, PhOCH2CH2OH,o‐CH3OC6H4CH2OH, or PhSCH2CH2OH with Cp2ZrCl2in the presence of NEt3gave series monomeric complexes Cp2ZrClX (X = OCH2CH2OCH3(1), OCH2CH2OPh (2),o‐OCH2C6H4OCH3(3) or OCH2CH2SPh (4)). In a reaction of Cp2TiCl2with PhSCH2CH2OH in the presence of NEt3, the complex Cp2TiCl(OCH2CH2SPh) (5) was obtained. These complexes were characterized by the1H and13C NMR, and the chemical shifts of the Cp rings for complexes1–4are nearly identical, despite differences in ligands for an indication of similar structures of these complexes around the metal center. Complex4crystallizes into the monoclinic P21/c space group with a = 13.806(3) Å, b = 16.394(3) Å, c = 7.838(2) Å, β = 100.85(3)° Z = 4, R = 0.029, Rw= 0.044, and Gof = 1.19. The molecular structure of complex4shows that the 2‐(phenylthio)ethoxide bonds to the Zr metal center through the alkoxide donor leaving the thioether donor free from