R. Contreras et al., PLATINUM(II) COMPLEXES WITH DITHIOLATES AND PHOSPHINITES AS LIGANDS -CRYSTAL-STRUCTURE OF [PT(S2CO)(P(OME)PH(2))(2)], Polyhedron, 15(2), 1996, pp. 183-190
Reaction of the complex [PtCl{P(O)Ph(2)} {P(OH)Ph(2)}(2)] with silver
or thallium derivatives of dithiolate ligands led to neutral complexes
of general formula [Pt{S-S} {P(O)Ph(2)} {P(OH)Ph(2)}], where {S-S}(-)
={S(2)CNEt(2)}(-) (1), {S2P(OEt)2}(-) (2) and {S(2)COEt}(-) (3). Comp
lexes 2 and 3 reacted with an excess of NaI in acetone solution by dea
lkylation of the coordinated dithiolate ligand and formation of the co
mpounds [Pt{S2P(O) (OEt)} {P(O)Ph(2)} {P(OH)Ph(2)}] Na (4) and [Pt{S2C
O}{P(O)Ph(2)}{P(OH)Ph(2)}] Na (5), respectively. The corresponding tet
raphenylphosphonium derivatives (6, 7) were prepared by a metathetical
reaction of these complexes with Ph(4)PBr in acetone solution. Relate
d dithiolate complexes were obtained by reaction of the complex [Pt{S-
S}(2)] with P(OMe)Ph(2) in molar ratio 1:2. Thus, the reaction of [Pt{
S(2)COEt}(2)] in dichloromethane solution at room temperature gave [Pt
{S(2)COEt} {P(OMe)Ph(2)}(2)] Cl (8). This complex reacted with NaI in
acetone to form the neutral compound [Pt{S2CO} {P(OMe)Ph(2)}(2)] (9).
When the reaction was carried out in dichloromethane at reflux tempera
ture using [Pt{S2P(OEt)(2)}(2)] as starting material, the neutral comp
ound [Pt{S2P(O)(OEt)} {P(OMe)Ph(2)}(2)] (10) was obtained. The crystal
structure of the complex 9 has been determined by X-ray diffraction.
The neutral complex shows a nearly square-planar coordination of the m
etal and a planar dithiocarbonate ligand.