Synthesis and Electrochemistry of Heterobridged Gold(I) and Gold(II) Complexes of Pyridine-2-thiolate. Crystal Structures of (μ-C5H4NS)> and (μ-C5H4NS)Br2>

Article abstract of DOI:10.1039/DT9950002245

The reaction of 2> or 2 with n(μ-C5H4NS)_n> led to the heterobridged dinuclear complexes (μ-C5H4NS)> or ClO4.The structure of (μ-C5H4NS)> has been established by X-ray crystallography and exhibits a short intramolecular gold-gold distance of 2.8623(7) Angstroem, whereas the shortest intermolecular distance is 3.984 Angstroem.The complex crystallized in the monoclinic space group P2₁/n with a = 9.430(2), b = 8.819(2), c = 22.786(5) Angstroem, β = 99.08(3) deg, Z = 4.Cyclic voltammograms showed that this complex is irreversibly oxidised at a platinum electrode; chemical oxidation with the ferrocenium ion in the presence of halide or pseudohalide ions gave the gold(II) complexes (μ-C5H4NS)X2> (X = Cl, Br, I or SCN).The same derivatives can be obtained by oxidative addition of halogen and/or by subsequent substitution with other halogens or pseudohalogens.The complex (μ-C5H4NS)Br2> crystallized in the triclinic space group P<*> with a = 14.810(10), b = 14.908(10), c = 17.041(12) Angstroem, α = 70.20(5), β = 69.77(5), γ = 89.19(5) deg, Z = 6 (at -100 deg C).The Au-Au bond lengths in the three independent molecules are 2.564(4), 2.548(4) and 2.547(4) Angstroem.

Full text of DOI:10.1039/DT9950002245

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