(Phosphine)gold(I) Complexes of Benzenedithioles. Crystal structures of 1,2‐benzenedithiolato‐bis[triphenyl‐phosphinegold(I)] and bis(triethylphosphine)gold(I) bis(1,2‐benzenedithiolato)gold(III)

The reaction of 1,2‐ and 1,3‐benzenedithiol C₆H₄(SH)₂ with chloro(phosphine)gold(I) complexes R₃PAuCl (R = Et, Ph) in the presence of triethylamine in tetrahydrofuran gives stable gold(I) complexes 1,2‐C₆H₄(SAuPR₃)₂ [R = Et (1) and Ph (2)] or 1,3‐C₆H₄(SAuPPh₃)₂ (3), respectively, in high yield. The compounds have been characterized by analytical and NMR spectroscopic data. From the reaction of 1,2‐C₆H(SH)₂ with Et₃PAuCl a by‐product [(Et₃P)₂Au]⁺ [Au(1,2C₆H₄S₂)₂]⁻ (4) has also been isolated in low yield. The crystal structures of compounds 2 and 4 have been determined by single crystal X‐ray diffraction. The gold(I) atoms in complex 2 are two‐coordinate with bond angles SAuP of 175.2(1) and 159.5(1)°, AuS bond distances of 2.304(1) and 2.321(1) å, and a short Au…Au contact of 3.145(1) Å. The gold(I) atom in the cation of complex 4 is also linearly two‐coordinate with a PAuP angle of 170.1(1) Å and AuP distances of 2.296(3) and 2.298(3) Å. The geometry of the anion in 4 shows a square‐planar coordination of gold(III) by two chelating 1,2‐benzenedithiolate ligands with AuS distances between 2.299(3) and 2.312(3) Å (for two crystallographically independent, centrosymmetrical anions in the unit cell).