Lithium, titanium and vanadium dithiocarboxylates

Reaction of the in situ generated lithium aryls 2,6-Mes2C6H3Li and 2,6-Trip2C6H3Li (Mes = 2,4,6-trimethylphenyl, Trip = 2,4,6-triisopropylphenyl) with CS2 afforded the lithium dithiocarboxylates [2,6-Mes2C6H3CS2]Li and [2,6Trip2C6H3CS2]Li in good yields. These sterically-hindered S-donor ligands proved useful for the salt-metathesis preparation of the paramagnetic Ti(III) and V(III) derivatives [2,6-Mes2C6H3CS2]TiCl2(thf)2 and [2,6Trip2C6H3CS2]2VCl(L)2(L = thf, py). Similarly, reaction of [2,6-Trip2C6H3CS2]Li with TiCl4(thf)2 in the presence of py afforded the diamagnetic Ti(IV)[2,6-Trip2C6H3CS2]2TiCl2(py). Single-crystal X-ray diffraction studies are reported for [2,6-Mes2C6H3]Li(OEt2)2, [2,6-Mes2C6H3CS2]TiCl2(thf)2, [2,6-Trip2C6H3CS2]2TiCl2(py), and [2,6Trip2C6H3CS2]2VCl(py)2.