Synthesis and characterisation of Group 4 metallocene alkoxide complexes. X-ray crystal structure of Cp*2ZrCl(OCH2CH2SPh)

Halo-alkoxide zirconocene complexes (η5-C5Me5)2ZrCl(OCH2CH2SPh) (1) and (η5-C5Me5)2ZrCl(OC6H4SH) (2) have been prepared by reaction of the corresponding zirconocene dichloride with HOCH2CH2SPh or HOC6H4SH, respectively, in the presence of NEt3. The molecular structure of 1 has been determined by X-ray diffraction studies. Alkyl- and aryl-containing species (η5-C5Me5)2ZrMe(OCH2CH2SPh) (3) and (η5-C5Me5)2ZrPh(OCH2CH2SPh) (4) were synthesised by reaction of the corresponding dialkyl or diaryl species with HOCH2CH2SPh, or by reaction of complex 1 with LiMe or LiPh, respectively. Finally, the dialkoxide complexes L2M(OCH2CH2SR)2 [L=η5-C5H5, M=Ti, R=Ph (5); L=η5-C5Me5, M=Ti, R=Ph (6); L=η5-C5Me5, M=Ti, R=Me (7)] were prepared by reaction of the appropriate dichloride and alcohol in the presence of NEt3, and (η5-C5H5)2Zr(OCH2CH2SMe)2 (8) was synthesised by reacting (η5-C5H5)2ZrMe2 with two equivalents of HOCH2CH2SMe.