Metal thiolate complexes are commonly prepared by reactions of metal complexes with thiols (RSH), thiolates (RS), and disulfides (RS). The salt metathesis reaction route is common.  In this method, an alkali metal thiolate is treated with a transition metal halide to produce an alkali metal halide and the metal thiolate complex:
:LiSCH + CuI → Cu(SCH) + LiI
Lithium tert-butylthiolate reacts with MoCl to give the tetrathiolate complex:
:MoCl + 4 t-BuSLi → Mo(t-BuS) + 4 LiCl
Mo(t-BuS) is a dark red diamagnetic complex that is sensitive to air and moisture. The molybdenum center has a distorted tetrahedral coordination to four sulfur atoms, with overall D symmetry.
Nickelocene and ethanethiol give a dimeric thiolate, one cyclopentadienyl ligand serving as a base:
:2 HSCH + 2 Ni(CH) → [Ni(SCH)(CH)] + 2 CH
Regarding their mechanism of formation from thiols, metal thiolate complexes can arise via deprotonation of thiol complexes.