Monocyclopentadienyltitanium complexes with thiolate ligands; crystal structure of Ti(η⁵-C₅H₅)(SC₆H ₅)₃

Thallium(I) derivatives of monocyclopentadienylbis(ethane-1,2-dithiolato)titanium, TlTi(?⁵-C₅H_nMe_5-n)(edt) ₂ {1, n = 0; 2, n = 4; edt = 1,2-S₂C₂H₄}, have been synthesised and isolated in yields of 81 and 45%, respectively, from reactions of the corresponding reagents, Ti(?⁵-C₅H_nMe_5-n)Cl₃ and thallium salts of the ethane-1,2-dithiol. Conformational changes of the chelating dithiolate ligands in compound 1 have been monitored by variable temperature ¹H-NMR spectroscopy. The preparation of compounds of the type TiCp(SAr)₃ (Cp = ?⁵-C₅H₅) has been investigated and the crystal structure of TiCp(SC₆H₅)₃, 3, determined by X-ray diffraction; the compound adopts a three-legged piano stool coordination geometry with two parallel phenyl rings (interplanar angle 2.0(2)°) directed away from the cyclopentadienyltitanium unit with inter-ring C-C contacts in the range 3.52-3.62 Å; the third phenyl ring is approximately orthogonal to the other two and lies over a cyclopentadienyl ring of a neighbouring molecule with an intermolecular C-C contact of 3.373(16) Å. © 1999 Elsevier Science S.A. All rights reserved.