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

Halo-alkoxide zirconocene complexes (eta(5)-C5Me5)(2)ZrCl(OCH2CH2SPh) (1) a nd (eta(5)-C5Me5)(2)ZrCl(OC6H4SH) (2) have been prepared by reaction of the corresponding zirconocene dichloride with HOCH2CH2SPh or HOC6H4SH, respect ively, in the presence of NEt3. The molecular structure of 1 has been deter mined by X-ray diffraction studies. Alkyl- and aryl-containing species (eta (3)-C5Me5)(2)ZrMe(OCH2CH2SPh) (3) and (eta(5)-C5Me5)(2)ZrPh(OCH2CH2SPh) (4) were synthesised by reaction of the corresponding dialkyl or diaryl specie s with HOCH2CH2SPh, or by reaction of complex I with LiMe or LiPh, respecti vely. Finally, the dialkoxide complexes L2M(OCH2CH2SR)(2) [L = eta(5)-C5H5, M = Ti, R = Ph (5); L = eta(5)-C5Me5, M = Ti, R = Ph (6); L = eta(5)-C5Me5 , M = Ti, R = Me (7)] were prepared by reaction of the appropriate dichlon' de and alcohol in the presence of NEt3, and (eta(5)-C5H5)(2)Zr(OCH2CH2SMe)( 2) (8) was synthesised by reacting (eta(5)-C5H5)(2)ZrMe2 with two equivalen ts of HOCH2CH2SMe. (C) 2000 Elsevier Science S.A. All rights reserved.