Activation of a Hydroamination Gold Catalyst by Oxidation of a Redox-Noninnocent Chlorostibine Z‑Ligand

In search of new platforms that support redox-controlled catalysis, we have investigated the noninnocent behavior of chlorostibine ligands coordinated to gold. The gold chlorostibine complex ((o-(Ph2P)­C6H4)2SbCl)­AuCl (1-Cl) undergoes a clean oxidation reaction on treatment with PhICl2. This oxidation reaction affords the corresponding trichlorostiborane complex ((o-(Ph2P)­C6H4)2SbCl3)­AuCl (2-Cl), which can be converted into the more tractable trifluoride analogue ((o-(Ph2P)­C6H4)2SbF3)­AuCl (3-Cl) by treatment with a fluoride source. As supported by experimental and computational results, these complexes possess a Au→Sb donor–acceptor interaction which is distinctly stronger in the oxidized complexes 2-Cl and 3-Cl. Both 1-Cl and 3-Cl undergo a clean chloride abstraction reaction to afford the corresponding cationic gold species [((o-(Ph2P)­C6H4)2SbCl)­Au]+ ([1]+) and [((o-(Ph2P)­C6H4)2SbF3)­Au]+ ([3]+), which have been isolated as SbF6– salts. As a result of a stronger Au→Sb interaction, cation [3]+ features a more Lewis acidic gold center. It forms an isolable water adduct and also activates terminal alkynes toward hydroamination with arylamines. These results demonstrate that the redox state of noninnocent Z-ligands can be used to control the catalytic activity of the adjoining metal center.