Halo-alkoxide zirconocene complexes (η 5 -C 5 Me 5 ) 2 ZrCl(OCH 2 CH 2 SPh) (1) and (η 5 -C 5 Me 5 ) 2 ZrCl(OC 6 H 4 SH) (2) have been prepared by reaction of the corresponding zirconocene dichloride with HOCH 2 CH 2 SPh or HOC 6 H 4 SH, respectively, in the presence of NEt 3 . The molecular structure of 1 has been determined by X-ray diffraction studies. Alkyl- and aryl-containing species (η 5 -C 5 Me 5 ) 2 ZrMe(OCH 2 CH 2 SPh) (3) and (η 5 -C 5 Me 5 ) 2 ZrPh(OCH 2 CH 2 SPh) (4) were synthesised by reaction of the corresponding dialkyl or diaryl species with HOCH 2 CH 2 SPh, or by reaction of complex 1 with LiMe or LiPh, respectively. Finally, the dialkoxide complexes L 2 M(OCH 2 CH 2 SR) 2 [L=η 5 -C 5 H 5 , M=Ti, R=Ph (5); L=η 5 -C 5 Me 5 , M=Ti, R=Ph (6); L=η 5 -C 5 Me 5 , M=Ti, R=Me (7)] were prepared by reaction of the appropriate dichloride and alcohol in the presence of NEt 3 , and (η 5 -C 5 H 5 ) 2 Zr(OCH 2 CH 2 SMe) 2 (8) was synthesised by reacting (η 5 -C 5 H 5 ) 2 ZrMe 2 with two equivalents of HOCH 2 CH 2 SMe.