Synthesis of Mono‐, Di‐, and Tri‐arylgold(III) Complexes Using Organomercury Compounds – Synthesis of the First Aurated Schiff Bases

The formylarylmercury(II) complex [Hg{C6H(CHO)‐6‐(OMe)3‐2,3,4}2] reacts with 4‐butylaniline (1:2) to give [Hg{C6H(CH=NC6H4C4H9‐4′)‐6‐(OMe) 3‐2,3,4}2] (1) by a condensation reaction. This complex reacts with Me4‐N[AuCl4] (1:1) to give [Hg{C6H(CH=NC6H4C4H9‐4′)‐6‐(OMe) 3‐2,3,4}Cl] (2) and the monoarylgold(III) compound cis‐ C6H4‐nBu‐4′)‐6‐(OMe)3‐2,3,4}Cl2] (3). This complex reacts with PPh3 (1:1) to give the adduct cis‐[Au{C6H(CH=NC6H4‐n, Bu‐4′)‐6‐(OMe)3‐2,3,4}Cl2(PPh3)] (4) and with AgClO4 (1:1) in acetone to give the ketonyl complex cis‐[ C6H4‐nBu‐4′)‐6‐ (OMe)3‐2,3,4}‐{CH2C(O)Me}Cl] (5). cis‐Me4N[Au(C6H4NO2‐2)2Cl 2] react with [Hg{C6H3(N=NC6H4OMe‐4′)‐2‐(OMe)‐5}Cl] and Me4NCl (1:1:1) to give cis‐[ C6H4OMe‐4′)‐2‐ (OMe)‐5}(C6H4NO2‐2)2] (6): Similarly, cis‐Me4N‐[Au(C6H4CF3‐2)2 Cl2] (7), obtained by treating [Hg(C6H4CF3‐2)2] with Me4N[AuCl4] and Me4NCl (1:1:1), reacts with [Hg(C6H4CH2NMe2‐2)Cl] and Me4NCl (1:1:1) to give the triarylgold(III) complex cis‐[ Me2‐2)(C6H4CF3‐2)2] (8). This complex can also be obtained by treating cis‐[ Me2‐2)Cl2] with [Hg(C6H4CF3‐2)2] and Me4NCl (1:1:1). The crystal structure of 3 reveals the presence of two independent molecules, in one of which the butylphenyl group is disordered. The geometry at the gold atom is square planar; distortions may be attributed to the narrow bite angle and steric repulsion between a chloride ligand and the ortho‐methoxy group. The greater trans influence of the aryl ligand causes a great difference in Au–Cl bond lengths.