Titanocene thiolates [Ti]Cl(SCHR-2- C4H3S) and [Ti](SCHR-2- C4H3S)2 (R = H, Me): Synthesis, properties and reaction chemistry

Titanocene dichloride, [Ti]Cl2 (1) ([Ti] = Ti(η5-C5H4SiMe3)2), with one equiv. of the lithium thiolates LiSCHR-2-cC4H3S (2a, R = H; 2b, R = Me) gave the appropriate [Ti](Cl)(SCHR-2-cC4H3S) compounds (3a, R = H; 3b, R = Me) under mild reaction conditions. Further treatment of 3a,b with another equiv. of thiolates 2a,b produced the respective bis(thiolates) species [Ti](SCHR-2-cC4H3S)2 (4a,b). Titanocenes 4a,b are also accessible, when 1 is reacted with 2a,b in a 1:2 M ratio. The hydrolysis reaction of 4a,b produced the titanoxane cluster 5, consisting of a [Ti′]6O9 cage ([Ti′] = Ti(η5-C5H4SiMe3)) with a silsesquioxane analog structure. The molecular structure of 5 in the solid state is the first example of a trigonal prismatic Ti6-polyhedron. Upon treatment of 4a,b with MCl2 (M = Pd, Pt), aiming to obtain heterobimetallic coordination complexes, however, either 1 or 3a,b were formed, depending on the reaction conditions. All the compounds have been characterized by elemental analysis, IR, NMR (1H, 13C{1H}) spectroscopy and mass-spectrometry.