Gold(I) as a Nucleophile - a Base

The ionization potentials of gaseous Group 11elements are similar, with Au(0) being 1.5 eV greater than the next highest member of the group, Cu(0). The ionization potentials are all very much greater than the alkali metals, making these ?coinage? elements rather unreactive to chemical oxidation. Ionization from the first oxidation state shows a different pattern, with Ag(I) being the most difficult of the Group 11 ions to lose an electron. Gold(I) is noble and only normally oxidized in the presence of strongly coordinating ligands such as thiols or cyanide. Gold(I) compounds are 2-, 3- and 4- coordinate, with 3-coordinate species generally showing visible photoluminescence under UV excitation. Dinuclear Au(I) compounds with strongly coordinating S or C ligands can be oxidized to form isolable metal-metal bonded Au(II) compounds which are often readily isolable. Many have been structurally characterized. T he ease with which electrons are lost from closed shell dinuclear sp ecies (with anti-bonding M-M interactions) increases when metalmetal bonded compounds are formed. T his observation was made by our group with oxidative-addition studies of dinuclear gold(I) ylide complexes. It was superbly demonstrated recently by Cotton?s group who reported the isolation and characterization of a dinuclear closed shell transition metal species which is more readily oxidized than cesium. Trinuclear Au(I) pyrazolates, TR(pz), carb eniates, TR(carb), and benzylimidazolates, TR(bz), are well known and undergo electron loss through oxidative addition forming Au(I,III) mixed valence species and ultimately trinuclear Au(III) species. Au(II) species are absent from isolation in these oxidations. These carbeniates and benzylimidazolates also are excellent bases for metals ions such as Tl(I) and Ag(I). The acidic, neutral trinuclear compound [Hg(C6F4)3]3 also interacts with these bases. We have also shown that the neutral organic pi acids C6F6 and TCNQ form stacked pi-acid pi-base products with the trinuclear Au(I) compounds. In this paper, the structure of the octafluoronaphthalene acid-base product will be described. It displays a feature not observed previously in that the product is photoluminescent with a bright yellow emission. The 3.5 ms lifetime is very long and reminiscent of the long lifetimes observed by Balch for the stacked methyl,methoxy Au(carb). The electrochemical oxidation of tetragold(I) clusters, [Au4(form)4] have been studied in 0.1 M Bu4NPF6/CH2Cl2 at Pt working electrode at different scan rates. Three waves are obtained at 0.75, 0.95, and 1.09 V vs Ag/AgCl at scan rate 500 mV/s. The potential of the three reversible waves is independent of the scan rate in the range 50 mV/s to 3 V/s. The current at the third wave is larger than those at the first two waves. These tetranuclear species app ear to be effec tive catalyst precursors for the oxidation in air of CO. Introduction. The electronic structural relationships of the coinage elements and the alkali metals are similar in the sense that each have a [closed shell]ns1 configuration, yet their ionization energies (Table) and chemistries are clearly vastly different. The Group 11coinage elements have an underlying nd10 level immediately below the ns1 level. Unlike the alkali elements, ionization leaves the filled d electron shell the next accessible for further ionization. The coinage elements are all relatively ?noble?, much less reactive to environm ental conditions than the alkali metals. With the coinage elements, oxidation becomes very much dependent upon the types of ligand s availab le to bo nd to the ionized state.