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

Titanocene dichloride, [Ti]Cl-2 (1) ([Ti] = Ti(eta(5)-C5H4SiMe3)(2)), with one equiv. of the lithium thiolates LiSCHR-2-(C4H3S)-C-c (2a, R = H; 2b, R = Me) gave the appropriate [Ti](Cl)(SCHR-2-(C4H3S)-C-c) 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-(C4H3S)-C-c)(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'](6)O-9 cage ([Ti'] = Ti(eta(5)-O5H4 SiMe3)) with a silsesquioxane analog structure. The molecular structure of 5 in the solid state is the first example of a trigonal prismatic Ti-6 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 (H-1, C-13{H-1}) spectroscopy and mass-spectrometry. (C) 2018 Elsevier Ltd. All rights reserved.