A stable gold(I)–enyne species obtained by alkyne carboauration in a complex rearrangement

An unprecedented tetranuclear gold derivative with unusual gold-enyne moieties is prepared by a mild and neat rearrangement of a dinuclear gold complex with a bridging bis(diphenylphosphino)alkyne and terminal alkynyl ligands. The complex originates as a consequence of an intramolecular addition of the AuC[triple bond, length as m-dash]CTol fragment to the internal diphosphine triple bond Ph2PC[triple bond, length as m-dash]CPPh2. The crystal structure of the tetranuclear complex shows a dinuclear metallacycle with a very short Au⋯Au bond interaction and bridging phosphino–enyne ligands. This disposition clearly stabilises the elusive vinyl gold species omnipresent as intermediates in gold-catalysed reactions.Financial support was provided by the Ministerio de Economía y Competitividad-FEDER (CTQ2016-75816-C2-1-P) and Gobierno de Aragon-Fondo Social Europeo FSE (E77).Peer reviewe