Cycloaurated triphenylphosphine-sulfide and -selenide

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 (AuCl₂(2-C₆H₄P(S)Ph₂) was synthesised in good yield by transmetallation of the organomercury precursor Hg(2-C₆H₄P(S)Ph₂)₂ with Me₄N[AuCl₄]. A route to the chloro-mercury analogue ClHg(2-C₆H₄P(S)Ph₂) was developed by reaction of the cyclomanganated triphenylphosphine sulfide (CO)₄Mn(2-C₆H₄P(S)Ph₂) with HgCl₂; this mercury substrate was also used in the synthesis of AuCl₂(2-C₆H₄P(S)Ph₂). The cycloaurated triphenylphosphine selenide complex AuCl₂(2-C₆H₄P(Se)Ph₂) was synthesised by an analogous methodology using the new phosphine selenide Hg(2-C₆H₄P(Se)Ph₂)₂ [prepared from Hg(2-C₆H₄PPh₂)₂ and elemental Se under sonication]. The phosphonamidic analogue AuCl₂(2-C₆H₄P(S)(NEt₂)₂) has also been synthesised from PhP(S)(NEt₂)₂via lithiation and mercuration. X-Ray crystal structures of several compounds are reported, and show the presence of puckered ring systems.