Synthesis, characterizations, and structure of group 4 metallocene complexes of some difunctional ligands containing oxygen and sulfur donors

Reactions of CH3OCH2CH2OH, PhOCH2CH2OH, o-CH3OC6H4CH2OH, or PhSCH2CH2OH wit h Cp2ZrCl2 in the presence of NEt3 gave series monomeric complexes Cp2ZrClX (X = OCH2CH2OCH3 (1), OCH2CH2OPh (2), o-OCH2C6H4OCH3 (3) or OCH2CH2SPh (4) ). In a reaction of Cp2TiCl2 with PhSCH2CH2OH in the presence of NEt3, the complex Cp2TiCl(OCH2CH2SPh) (5) was obtained. These complexes were characte rized by the H-1 and C-13 NMR, and the chemical shifts of the Cp rings for complexes 1-4 are nearly identical, despite differences in ligands for an i ndication of similar structures of these complexes around the metal center. Complex 4 crystallizes into the monoclinic P2(1)/c space group with a = 13 .806(3) Angstrom, b = 16.394(3) Angstrom, c = 7.838(2) Angstrom, beta = 100 .85(3)degrees, Z = 4, R = 0.029, R-w = 0.044, and Gof = 1.19. The molecular structure of complex 4 shows that the 2-(phenylthio)ethoxide bonds to the Zr metal center through the alkoxide donor leaving the thioether donor free from coordination.