The first anionic arenediethynylgold(I) complexes

We report synthetic methods for the preparation of mono-, di-, tri- and polyanionic alkynylgold(I) complexes, derived from diethynylarenes. The reaction between PPN[Au(acac)2] and 1,3-diethynylbenzene [HCC(mphen)CCH] (1:1 M ratio) afforded the polymeric complex (PPN)n[Au{CC(mphen)CC}]n (1) while the monomeric complexes (PPN)[Au{CC(Ar)CCH}2] [Ar=mphen (2), mes (3)] resulted when the same dialkyne or 1,3-diethynylmesitylene [HCC(mes)CCH] were used in a 1:2 M ratio. Complexes PPN[XAuCC(Ar)CCH] [Ar=mphen, X=Cl (4), Ar=mes, X=Cl (5), SCN (6)] were obtained from the metathesis reactions between complexes 2 or 3 and the appropriate PPN[AuX2] salts. The CCH groups in complexes 2 or 4 are acidic enough as to react with [Au(acac)PPh3] (1:2) or with PPN[Au(acac)2] (1:1) to give complexes PPN[Au{CC(mphen)CCAuPPh3}2] (7) or (PPN)3[Au{CC(mphen)CCAuCl}2] (8), respectively. Complexes (PPN)2[XAuCC(Ar)CCAuX)] [Ar=mphen, X=Cl (9); Ar=mes, X=Cl (10), SCN (11)] have been prepared by reacting [Ph3PAuCC(mphen)CCAuPPh3] with PPN[AuCl2] (1:2) (9) or [AuCC(mes)CCAu]n with the appropriate PPNX (1:2) salt (10, 11).