A fixation mode of gold from solutions using heterogeneous reaction of cadmium dicyclohexyl dithiophosphate with H[AuCl4]. Structural and (13C, 31P) CP/MAS NMR studies and thermal behaviour of crystalline polymeric gold(I) dicyclohexyl dithiophosphate and

Two novel compounds: polynuclear catena-poly[bis(μ3-O,O′-di-cyclo-hexyldithiophosphato-S,S,S′)digold(I)] (AuAu) (1) and crystalline bis(O,O′-di-cyclo-hexylthiophosphoryl)disulphide, (cyclo-C6H11O)2P(S)SS(S)P(O-cyclo-C6H11)2 (2) were prepared using heterogeneous reaction between freshly precipitated binuclear cadmium(II) dithiophosphate (Dtph), [Cd2{S2P(O-cyclo-C6H11}4] and H[AuCl4] in 2 M hydrochloric acid. The isolated compounds 1 and 2 (the fixation mode of gold from the solution and the oxidised form of Dtph groups, respectively) have been studied by means of single-crystal X-ray diffraction, 13C and 31P cross-polarisation/magic-angle-spinning (CP/MAS) NMR spectroscopy and simultaneous thermal analysis (STA). Centrosymmetric binuclear molecule of 1, [Au2{S2P(O-cyclo-C6H11)2}2] comprises a pair of μ-bridging di-cyclo-hexyl Dtph ligands, linking two neighbouring gold atoms, and displays additional intramolecular aurophilic bond Au⋯Au. At the supramolecular level of structural self-organisation of complex 1, infinite polymeric zigzag chains arise due to pairs of the secondary bonds Au···S between neighbouring binuclear molecules. Centrosymmetric molecule of 2 displays two O,O′-di-cyclo-hexythiophosphoryl fragments, which are connected by the chemical bond S(1)S(1)a, and a planar zigzag array [SPSSPS] passing through the central part of the molecule. To characterise additionally the Dtph groups in both compounds 1 and 2, chemical shift anisotropy (CSA) parameters (δaniso and η) were calculated from spinning sideband manifolds in experimental 31P MAS NMR spectra. The thermal behaviour of complex 1 was studied using simultaneous thermal analysis (a combination of TG and DSC) under an argon atmosphere. The thermal behaviour displays stepwise mass loss, comprising thermal decompositions of the organic and inorganic parts of 1 with gold(I) dithio-meta-phosphate and reduced metallic gold as the intermediate and the final products, respectively.

► Doubly-bridged binuclear gold(I) di-cyclo-hexyldithiophosphate comprising aurophilic bonds.
► Supramolecular self-organisation of polymeric chains involving secondary bonds Au⋯S.
► Thermal decomposition of the complex successively yields [Au2(S2PO)2] and metallic Au.
► Centrosymmetric molecule of bis(O,O′-di-cyclo-hexylthiophosphoryl) disulphide.
► 13C and 31P CP/MAS NMR characteristics of di-cyclo-hexyldithiophosphate compounds.