Polymeric gold(I) diisobutyl dithiophosphate, [Au2{S2P(O-iso-C4H9)2}2]n: Synthesis, supramolecular self-organization (a role of aurophilic interaction), 13C and 31P MAS NMR spectroscopy, and thermal behavior

Abstract

A new polymeric gold(I) diisobutyl dithiophosphate (Dtph), [Au2{S2P(O-iso-C4H9)2}2]n (I), was preparatively obtained and characterized by 13C and 31P MAS NMR spectroscopy and X-ray diffraction (CIF file CCDC no. 977818). Diagrams of the χ2 statistic were constructed from the complete 31P MAS NMR spectra and used to calculate the 31P chemical shift anisotropy (δaniso = δzz − δiso) and the asymmetry parameter η = (δyy − δxx)/(δzz − δiso). The main structural unit of complex I is the noncentrosymmetric dinuclear molecule [Au2{S2P(O-iso-C4H9)2}2], in which the gold atoms are linked by two bridging ligands Dtph. The central cyclic structural fragment of the dimer [Au2S4P2] is additionally stabilized by the intramolecular aurophilic interaction Au⋯Au. Further supramolecular self-organization of the complex involves intermolecular aurophilic bonds Au⋯Au that serve to unite adjacent dinuclear molecules [Au2{S2P(O-iso-C4H9)2}2] with different spatial orientations into the polymer chains ([Au2{S2P(O-iso-C4H9)2}2])n. The thermal behavior of complex I was examined by synchronous thermal analysis under argon. The character of the thermolysis of the complex to reduced metallic gold as a final product was determined.