Dithiophosphinate complexes

Dithiophosphinate complexes, osmium, 37 294 Dithiopyrocatechin, complexes of, 3 277 Dithiotreitol, 45 265... 

Dithiophosphinate complexes [V(S2PX2)3] (X = F, CF3, Me, Ph, OEt) were reported293 and the structure where X = OEt has been determined.294 The six sulfur atoms form a trigonally distorted octahedron around vanadium with the average V—S distance 2.45 0.02 A. Visible spectra (in CH2C12 or an oriented crystal) show four bands a charge-transfer band is observed at 22700 and 23 300 cm-1 in the solution and crystal. The others at 12 820, 18080 and 26 400 cm-1 (13 200, 18 400 and 26 400 in the crystal) are the expected transitions for octahedral V111. 

The tetrakis-dithiophosphinate complex [PPI14][Pr(S2PMe2)4], whose crystal structure has also been determined, has a distorted tetragonal antiprismatic geometry with Pr—S = 2.888-3.0150.400 The complex ions [M S2P(OEt)2 4]", have been the subject of an NMR paramagnetic shift study (see Section 39.2.9.4). 

Polymeric dithiophosphinate complexes of the type (134 M = Zn or Cd) have been obtained.922 These complexes add py readily and reversibly to yield polymeric octahedral complexes. 

R2P - (R = alkyl, aryl, F) S IPdLJ Dithiophosphinate complexes. These form 1 1 and 1 2 tertiary phosphine adducts [Pd( j,-S2PR2XtJ2-S RjXPR])] and [Pd(t,2-S2PR2)(PRy2][R2PSJ 27... 

Boehme, C., Wipff, G. 2001. The energetic and structural effects of steric crowding in phosphate and dithiophosphinate complexes of M3+ lanthanide cations. A computational study. Chem. Eur. J. 1 1398-1407. 

Dithiocarbamate and dithiophosphinate complexes have important uses. The former are used as fungicides and for solvent extraction and the latter as high pressure lubricants. Dithiocarbamates stabilize high oxidation states as in [FeIV(dtc)3]+ or [NiIV(dtc)3]+. Although dithiocarbamates are usually made from sodium salts such as NaS2CNMe2 or by oxidations using thiuram disulfides, they can also be made by insertion reactions of CS2 with dialkylamides, for example,... 

The interaction of VO(S2AsMc2) with Lewis bases is entirely analogous to that of the dithiophosphinate complex (Vol. 4, p. 59). Equilibria are established in which at first one and then two molecules of base occupy co-ordination positions vacated by the S atoms of the thioarsinate ligands. Complete displacement of these ligands occurs at very high base concentrations. 

Also reported are dithiophosphinate complexes of the type (57 M = Pd R = F, Me, Et, CF3 or OEt). A correlation was observed between the Pd— stretching frequencies and the first electronic transition, and the substituents... 

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