Transition metal thiolate complex

From the electric structure perspective, thiolate is a pi-donor ligand, akin to alkoxide.

For example, Mo(t-BuS)4, a dark red diamagnetic solid, is sensitive to oxygen and moisture.

Unsaturated versions of 1,2-dithiolates usually take the form of dithiolene ligands, the parent member being (HC)2S22-.

Synthetic analogues can be prepared by combined redox and salt metathesis reactions:[7] Thiolates are relatively basic ligands, being derived from conjugate acids with pKa's of 6.5 (thiophenol) to 10.5 (butanethiol).

Thiolate ligands, especially when nonbridging, are susceptible to attack by electrophiles including acids, alkylating agents, and oxidants.

Metal thiolate functionality, almost always provided by the cysteine residue, is pervasive in metalloenzymes.

The pi-donor property of thiolate ligands stabilizes Fe(IV) states in the enzyme cytochrome P450.

Structure of the quasi-two-coordinate ferrous dithiolate Fe[SC 6 H 3 -2,6-(C 6 H 2 -2,4,6-( i Pr) 3 ) 2 ] 2 . [ 1 ]
Mo( t -BuS) 4 .
Structure of Fe 2 (SCH 3 ) 2 (CO) 6 .