Preparation and Crystal Structures of Gold(I) Complexes of a Series of Benzenethiolates: Pair Formation by Gold‐to‐Gold Interactions of (Benzenethiolato)(triphenylphosphane)gold(I)

Masami Nakamoto, Wolfgang Hiller, Hubert Schmidbaur

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Abstract

Chloro(triphenylphosphane)gold(I) reacts readily with benzenethiol C6H5SH and a series of sterically hindered (2,4,6‐trialkylbenzene)thiols 2,4,6‐R3C6H2SH in the presence of NEt3 to yield stable gold(I) complexes Ph3PAu(S – 2,4,6‐C6H2R3) [RH (1), Me (2), Et (3), iPr (4)]. The crystal structures of these complexes have been determined by single‐crystal X‐ray diffraction analysis. In all compounds the gold atoms are linearly two‐coordinate with very similar bond lengths and angles. – While complexes 2 – 4 with bulky thiolate ligands are monomeric in the crystal lattice, complex 1 has been found to form pairs of molecules with intermolecular gold – gold contacts of 313.5(5) pm. The Mössbauer spectra of the complexes exhibit large isomer shifts (I.S.), ranging from 3.06 to 3.72 mm s–1, and quadrupole splittings (Q.S.), ranging from 7.90 to 8.68 mm s–1. These data can be attributed to the strong electron‐donating properties of the benzenethiolate ligands. The gold – gold contacts in complex 1 lead to I.S. and Q.S. values which are slightly smaller than those of 2 – 4. The Au – S distances do not show a major influence of the S – Au – P pairing in complex 1 as compared to complexes 2 – 4.

Original languageEnglish
Pages (from-to)605-610
Number of pages6
JournalChemische Berichte
Volume126
Issue number3
DOIs
StatePublished - Mar 1993
Externally publishedYes

Keywords

  • Gold(I) complexes
  • Gold(I) thiolates
  • Thiolato complexes

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