Aurophilicity-based one-dimensional arrays of gold(I) phenylene-1,3- and -1,4-dithiolates

Hendrik Ehlich, Annette Schier, Hubert Schmidbaur

Research output: Contribution to journalArticlepeer-review

36 Scopus citations

Abstract

Phenylene-1,3-dithiol is converted into a trinuclear gold complex by treatment with 1 equiv of {[(Ph3P)Au]3O}+BF4-. In the product, the phenylene unit bears one gold thiolate and one di(gold)sulfonium function. These components aggregate into one-dimensional arrays through head-to-tail aurophilic contacts between the two functions. In the association process, the Au-S-Au angle of the sulfonium group is opened up to accommodate the incoming gold atom between its metal centers. A similar mode of aggregation is found for the triply aurated biphenylene-4,4′-dithiol obtained using the tri(gold)oxonium salt with tri(p-tolyl)phosphine ligands. Probably for steric reasons, in this oligomerization process, the gold(I) thiolate unit is attached side-on to the digold sulfonium unit with retention of the small Au-S-Au angle. Under similar reaction conditions, and with the same molar ratio of the components, phenylene-1,4-dithiol is converted into the bis-sulfonium salt: 1,4-{[(p-Tol)3PAu]2S}2C6 H4(BF4)2, the dications of which also associate into chains. Along the chains, the phenylene spacers alternate with tetranuclear gold clusters which arise from intimate aggregation of pairs of gold atoms. Together with previous findings, the present results show that gold thiolate (-SAuL) and digold sulfonium functions [-S(AuL)2+] in proper orientation at an arene unit (α-ω) can be considered as "soldering" points which can be used for joining up the molecular units into one-dimensional arrays solely through metal-metal contacts, which appear to be operative even against Coulomb repulsion between cations. The reaction of biphenylene-4,4′-dithiol with 2 equiv of sodium methoxide and [tri-(c-hexyl)phosphine]gold chloride gives only neutral digold dithiolate complex 4 which is not associated owing to the steric bulk of the tri(c-hexyl)phosphine ligands.

Original languageEnglish
Pages (from-to)3721-3727
Number of pages7
JournalInorganic Chemistry
Volume41
Issue number14
DOIs
StatePublished - 15 Jul 2002
Externally publishedYes

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