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.
Synthesis, Structure, and Electrochemistry of the Ni−Au Carbonyl Cluster [Ni12Au(CO)24]3− and Its Relation to [Ni32Au6(CO)44]6− / I. Ciabatti; C. Femoni; M. C. Iapalucci; G. Longoni; S. Zacchini; S. Fedi; F. Fabrizi de Biani. - In: INORGANIC CHEMISTRY. - ISSN 0020-1669. - STAMPA. - 51:(2012), pp. 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.
