A detailed study of the reaction between [Ni6(CO)12]2− and [AuCl4]− afforded the isolation of the new Ni−Au cluster [Ni12Au(CO)24]3− as well as identifying an improved synthesis for the previously reported [Ni32Au6(CO)44]6−. The new [Ni12Au(CO)24]3− cluster is composed by two [Ni6(CO)12]2− moieties coordinated to a central Au(I) ion, as determined by Xray diffraction. It is noteworthy that the two [Ni6(CO)12]2− fragments display different geometries, i.e., trigonal antiprismatic (distorted octahedral) and distorted trigonal prismatic (monocapped square pyramidal). The chemical reactivity of these clusters and their electrochemical behavior have been studied. [Ni12Au(CO)24]3− is irreversibly transformed, upon electrochemical reduction, into Au(0) and [Ni6(CO)12]2−, followed by the reversible reduction of the latter homometallic cluster. Conversely, [Ni32Au6(CO)44]6− displays five reductions, with apparent features of reversibility, confirming the ability of larger metal carbonyl clusters to reversibly accept and release electrons.
I. Ciabatti, C. Femoni, M. C. Iapalucci, G. Longoni, S. Zacchini, S. Fedi, et al. (2012). Synthesis, Structure, and Electrochemistry of the Ni−Au Carbonyl Cluster [Ni12Au(CO)24]3− and Its Relation to [Ni32Au6(CO)44]6−. INORGANIC CHEMISTRY, 51, 11753-11761 [10.1021/ic301679h].
Synthesis, Structure, and Electrochemistry of the Ni−Au Carbonyl Cluster [Ni12Au(CO)24]3− and Its Relation to [Ni32Au6(CO)44]6−
CIABATTI, IACOPO;FEMONI, CRISTINA;IAPALUCCI, MARIA CARMELA;LONGONI, GIULIANO;ZACCHINI, STEFANO;
2012
Abstract
A detailed study of the reaction between [Ni6(CO)12]2− and [AuCl4]− afforded the isolation of the new Ni−Au cluster [Ni12Au(CO)24]3− as well as identifying an improved synthesis for the previously reported [Ni32Au6(CO)44]6−. The new [Ni12Au(CO)24]3− cluster is composed by two [Ni6(CO)12]2− moieties coordinated to a central Au(I) ion, as determined by Xray diffraction. It is noteworthy that the two [Ni6(CO)12]2− fragments display different geometries, i.e., trigonal antiprismatic (distorted octahedral) and distorted trigonal prismatic (monocapped square pyramidal). The chemical reactivity of these clusters and their electrochemical behavior have been studied. [Ni12Au(CO)24]3− is irreversibly transformed, upon electrochemical reduction, into Au(0) and [Ni6(CO)12]2−, followed by the reversible reduction of the latter homometallic cluster. Conversely, [Ni32Au6(CO)44]6− displays five reductions, with apparent features of reversibility, confirming the ability of larger metal carbonyl clusters to reversibly accept and release electrons.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
