Many thiolate complexes are prepared by redox reactions.  Organic disulfides oxidize low valence metals, as illustrated by the oxidation of titanocene dicarbonyl:
Some metal centers are oxidized by thiols, the coproduct being hydrogen gas:
These reactions may proceed by the oxidative addition of the thiol to Fe(0).
Thiols and especially thiolate salts are reducing agents. Consequently, they induce redox reactions with certain transition metals.  This phenomenon is illustrated by the synthesis of cuprous thiolates from cupric precursors:
:4 HSCH + 2 CuO → 2 Cu(SCH) + (CHS) + 2 HO
Thiolate clusters of the type [FeS(SR)] occur in iron–sulfur proteins.  Synthetic analogues can be  prepared by combined redox and salt metathesis reactions:
:4 FeCl + 6 NaSR + 6 NaSH → Na[FeS(SR)] + 10 NaCl + 4 HCl + HS + RS