__Journal otOrgano. metalliC Chemistry ELSEVIER Journal of Organometallic Chemistry 538 (1997) 83-90 Propylthiotetramethylcyclopentadienyl complexes of iron, titanium and zirconium. Structural characterization of "[ 15-C 5Me 4SCH 2CH 2CH 3" ---12 TiC12 Roland Broussier *, Cyrille Bourdon, Olivier Blacque, Alain Vallat, Marek M. Kubicki, Bernard Gautheron Laboratoire de Synthbse et d'Electrosynthbse Organom~talliques associ£ au CNRS, UMR 5632, 6 boulevard Gabriel, BP 138, 21004 Dijon Cedex, France Received 30 August 1996; revised 25 October 1996 Abstract The use of the propylthio substituted tetramethylcyclopentadienylsodium salt leads to octamethyl-l,l'-di(propylthio)ferrocene and dichlorodi(propylthiotetramethylcyclopentadienyl)zirconium or titanium(IV). The structure of ['q5-C 5Me4 SCH 2 CH2 CH 3]2 TiC12 has been • . . o 3 estabhshed by X-ray analysis (orthorhomblc, Pbca, a = 16.767(1), b = 16.247(3), c = 19.002(3)A, V = 5176.2(9)A, Z = 8, R F = 0.052). The complexes have been characterized by JH and 13C NMR and electrochemical studies. Keywords: Cyclopentadienyl; Sulphur; Ferrocene; Zirconium; Titanium 1. Introduction The association of early transition metals to electron-rich metals such as rhodium is of great interest because of the potential cooperative reactivity of two widely different metals. Among the various bridging modes via a heteroatom such as P or S we have been interested in bimetallic compounds in which the metal atoms are maintained close to each other by a short bridge as for [AsPh 4][(,qL CsMes)2Zr(Ix-S)2Rh(CO)2] [1]. In the presence of triphenylphosphine, this complex initiates the carbony- lation of ethene to give acrolein. We have also been interested in the preparation of bimetallic compounds in which the metal atoms are linked via a substituted cyclopentadienyl ring bearing a pendant functional group such as a phosphido group in Fe('q~-CsMeaPPh2)2M(CO)4, M = Cr, Mo, W [2]. By analogy, a linkage between two metallic centres using a cyclopentadienyl with a thioether substituent may be considered. As far as we know, chemistry in this field has been performed in the ferrocene series [3], * Corresponding author. Tel.: +03 80 39 61 03; Fax: +03 80 39 61 00. but no reports concerning the bent metallocenes have as yet appeared in the literature. The present work reports on the generation of thioether substituted cyclopentadienides and on the for- marion of the corresponding substituted metallocenes. 2. Results and discussion Sulphur substituted cyclopentadienyl ligands are pre- sent in chelating substituted ferrocenes such as Fe(~l 5- CsH4SR)2, Fe(-qS-CsH4SR)(-qS-CsHs) [3] and cy- clopentadienyl tricarbonyl manganese and rhenium compounds such as Mn('qS-CsH4SR)(CO)3 [4]. The sulfido groups have been introduced by the standard method of lithiation of the organometallic precursor. This synthetic strategy is not applicable to the synthesis of substituted bent metallocenes M('qS-CsH4SR)2C12 which incorporate a Group 4 transition metal, because of the inability to form substituted derivatives by ring- substitution routes. We have studied an alternative ap- proach consisting in the initial preparation of sulphur substituted cyclopentadienes and their transformation into the corresponding cyclopentadienides. In a follow- ing step, the metallocene products are obtained by 0022-328X/97/$17.00 Copyright © 1997 Elsevier Science S.A. All rights reserved. PH S0022-328X(96)06909-4