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.
