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Updated: Jun 13, 2026

Preparation and Reactivity of a Triphosphenium Bromide Salt: A Convenient and Stable Source of Phosphorus(I)
Published on: November 22, 2016
Cycloaurated triphenylphosphine-sulfide and -selenide
Kelly J Kilpin1, William Henderson, Brian K Nicholson
1Department of Chemistry, University of Waikato, Private Bag 3105, Hamilton, New Zealand.
Abstract:
The first examples of cycloaurated phosphine sulfides and triphenylphosphine selenide have been synthesised; these complexes are fairly rare examples of gold(iii) complexes with potentially reducing sulfur- and selenium-donor ligands. The cycloaurated complex (AuCl(2)(2-C(6)H(4)P(S)Ph(2)) was synthesised in good yield by transmetallation of the organomercury precursor Hg(2-C(6)H(4)P(S)Ph(2))(2) with Me(4)N[AuCl(4)]. A route to the chloro-mercury analogue ClHg(2-C(6)H(4)P(S)Ph(2)) was developed by reaction of the cyclomanganated triphenylphosphine sulfide (CO)(4)Mn(2-C(6)H(4)P(S)Ph(2)) with HgCl(2); this mercury substrate was also used in the synthesis of AuCl(2)(2-C(6)H(4)P(S)Ph(2)). The cycloaurated triphenylphosphine selenide complex AuCl(2)(2-C(6)H(4)P(Se)Ph(2)) was synthesised by an analogous methodology using the new phosphine selenide Hg(2-C(6)H(4)P(Se)Ph(2))(2) [prepared from Hg(2-C(6)H(4)PPh(2))(2) and elemental Se under sonication]. The phosphonamidic analogue AuCl(2)(2-C(6)H(4)P(S)(NEt(2))(2)) has also been synthesised from PhP(S)(NEt(2))(2)via lithiation and mercuration. X-Ray crystal structures of several compounds are reported, and show the presence of puckered ring systems.
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