Four different dialkyldithiophosphate (DTP) ions, (RO)(2)PSS- (R = C3H7, iso-C3H7, iso-C4H9, and cyclo-C6H11 ), have been adsorbed on the surface of synthetically prepared stibnite, Sb2S3, and studied by means of P-31 CP/MAS NMR. Corresponding individual [Sb{S2P(OR)(2)}(3)] complexes have also been synthesized and used for comparison with the surface-adsorbed DTP species. The results show that a low concentration of collector at the surface leads to a chemisorbed monolayer of DTP on the mineral surface. At high concentration of DTP, a surface precipitate of Sb(DTP)(3) is formed. P-31 CP/MAS NMR and chemical shift anisotropy data indicate that the S-P-S bite angle of the chemisorbed DTP groups on the surface is larger than in the corresponding precipitated complexes and the coordination of the ligands differs. Using single-crystal Xray diffraction technique, the molecular structure of a solvated form of crystalline O,O'-di-cyclo-hexyldithiophosphate antimony(III) complex has been resolved. In this novel molecular structure, the central antimony atom S,S'-anisobidentately coordinates three structurally non-equivalent DTP groups, and therefore, the geometry of the [SbS6] chromophore can be approximated by a distorted octahedron. Besides that, useful correlations between P-31 CSA parameters and structural data on this complex were also established. (C) 2011 Elsevier Inc. All rights reserved.