Gold( <scp>i</scp> ) alkoxide and thiolate complexes as potential atomic layer deposition precursors

Reactions of AuCl(PR₃) with NaOC(CF₃)₃ in the presence of 1 equiv. of Ag[BF₄] or Ag[PF₆] afforded the gold(I) alkoxide complexes [(Au{OC(CF₃)₃}{PR₃})_<i>n</i>] (R = Me (1), Et (2), ⁱPr (3) and ^<i>t</i>Bu (4)). In our hands, analogous reactions using NaO^<i>t</i>Bu (for R = ⁱPr) did not yield a thermally robust product. However, the thiolate complexes [{Au(S^<i>t</i>Bu)(PR₃)}_<i>n</i>] (R = Me (5) and ⁱPr (6)) were accessed by reaction of [{Au(S^<i>t</i>Bu)}_<i>n</i>] with PR₃. Compound 1 is a trimer featuring linear Au{OC(CF₃)₃}(PMe₃) units connected through unsupported aurophilic interactions, whereas more sterically hindered 3 and 4 are monomers in the solid state. Compound 5 is a dimer connected <i>via</i> an aurophilic interaction, while 6 is a monomer. In solution, 1 and 3 reacted almost instantly with HBpin or H₃SiPh to afford metallic gold and volatile byproducts (free PR₃ and H₂ accompanied by {(F₃C)₃CO}Bpin or a mixture of {(F₃C)₃CO}SiH₂Ph and {(F₃C)₃CO}₂SiHPh). By contrast, analogous reactions with thiolate complex 5 required over 24 hours to reach completion. Complexes 1-4 melted at 105-106, 19-21, 59-61 and 181-183 °C, respectively, and sublimed cleanly between 50 and 80 °C at 5 mTorr. By contrast, 5-6 decomposed (completely or partially) during attempted sublimation at 5 mTorr; in the case of 5, decomposition was shown to occur <i>via</i> phosphine dissociation to re-form [{Au(S^<i>t</i>Bu)}_<i>n</i>]. Of the complexes in this work, 3 offers the best combination of thermal stability and volatility, and the relatively low melting point is attractive. However, 3 was ∼4% decomposed after 72 h at 85 °C, and ∼10% decomposed after 96 h at 100 °C, forming soluble [Au(PⁱPr₃)₂][H{OC(CF₃)₃}₂] (7), gold metal, and other insoluble product(s). Preliminary ALD reactor experiments using 3 (with a delivery temperature of 85 °C) and HBpin showed gold deposition at 124 °C, and no deposition was observed at this temperature using 3 without HBpin.