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(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)
Authors:Masami Nakamoto  Huub Koijman  Martin Paul  Wolfgang Hiller  Hubert Schmidbaur
Abstract: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).
Keywords:Gold(I) benzenedithioles  Gold(III) benzenedithioles  (Phosphine)gold(I) complexes  Benzenedithiolato complexes
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