Tridentate Coordination Modes of Functionalized Titanocene Thiolates. Crystal Structure of [(η⁵-C₅H₄SiMe₃)Ti(μ-η⁵:κ-P-C₅H₄PPh₂)(μ-SPh)₂W(CO)₃]

Mixed monosubstituted cyclopentadienyl Ti(IV) derivatives [(η5-C5H4R)(η5-C5H4SiMe3)Ti(SPh)2] (R = PPh2, Ph2PO, Ph2PS) react with carbonylmetal fragments of group 6 to generate heterodinuclear compounds [(η5-C5H4SiMe3)Ti(μ-η5:κ-P-C5H4PPh2)(μ-SPh)2M(CO)3], [(η5-C5H4SiMe3)(SPh)Ti(μ-η5:κ-P-C5H4PPh2)(μ-SPh)M(CO)4], [(η5-C5H4P(E)Ph2)(η5-C5H4SiMe3)Ti(μ-SPh)2M(CO)4] (M = Mo, W; E = O, S) and [(η5-C5H4SiMe3)Ti(μ-η5:κ-E-C5H4P(E)Ph2)(μ-SPh)2M(CO)3] (M = Mo, W; E = S or M = Mo, E = O). All complexes have been characterized by spectroscopic data. The crystal structure of [(η5-C5H4SiMe3)Ti(μ-η5:κ-P-C5H4PPh2)(μ-SPh)2W(CO)3] has been determined by X-ray diffraction techniques, and it was confirmed that the titanium precursor acts as a tridentate metalloligand. The complex crystallizes in the orthorhombic system in space group Pna21; a = 23.081(2) Å, b = 14.3046(9) Å, c = 11.6892(8) Å; Z = 4.