Transition metal dithiophosphate complex


Transition metal dithiophosphate complexes are coordination compounds containing dithiophosphate ligands, i.e. ligands of the formula 2PS. The charge-neutral complexes tend to be soluble in organic solvents, especially when R is branched. Dithiophosphates are available with a wide variety of alkoxy groups. The range of complexes is similar to those for dithiocarbamate complexes.

Preparation

Dithiophosphate ligands are prepared by alcoholysis of phosphorus pentasulfide:
Dialkoxydithiophoric acids react with many metal oxides, chlorides, and acetates:
Alternatively, salts, such as ammonium diethyldithiophosphate, can be used to prepare complexes by salt metathesis reactions:
Oxidation of dithiophosphoric acid gives the disulfide. Dithiophosphate complexes have also be prepared by oxidative addition of these disulfides:

Ligand properties

Dithiophosphates, when bidentate, are classified as L-X ligands in the Covalent bond classification method. In the usual electron counting method, they are three-electron ligands. With respect to HSAB theory, dithiophosphates are classified as soft ligands. In addition to the conventional representation, they are also described by a zwitterionic resonance structure. Phosphorus is tetrahedral.

Selected homoleptic complexes

Homoleptic complexes have formulas,, and M2.
  • 3, red-brown,
  • , violet
  • , red
  • pink, paramagnetic
  • violet
  • yellow, diamagnetic
  • poly-
These complexes are almost always solids at room temperature.

Applications

Zinc dialkyldithiophosphates are components of oil additives. Dithiophosphate complexes are also implicated as intermediates in froth flotation, e.g. for the purification of copper from slag.