Heterodinuclear\nAuNi(CO)<sub><i>n</i></sub><sup>–</sup> (<i>n</i> = 2–3) Complexes Featuring\nan Anionic Au<sup>–</sup> as a Donor Ligand for Ni(CO)<sub><i>n</i></sub&g

The gas-phase heterodinuclear gold–nickel\ncarbonyl\nAuNi(CO)<sub><i>n</i></sub><sup>–</sup> (<i>n</i> =\n2–3) anion complexes were mass-selected and studied by using\nphotoelectron velocity-map imaging spectroscopy in combination with\nquantum-chemical calculations, which can establish both the geometries\nand electronic structures of these anions. These complexes are all\nconfirmed to be singlet ground states with one gold atom bonded at\nthe central nickel atom of the Ni(CO)<sub><i>n</i></sub> moieties. Further bonding analyses indicate that unlike the alkali-metals\nas covalently bonded ligands to form the electron-sharing alkali-metal–nickel\nbonding in the alkali-metal–nickel carbonyl anionic complexes,\nthe Au atom in the AuNi(CO)<sub><i>n</i></sub><sup>–</sup> complexes serves as a datively bound ligand for Ni(CO)<sub><i>n</i></sub> to form gold-to-nickel dative bonding.