The direct reactions of homometallic [Ni6(CO)12]2- and [Pt6(CO)12]2- Chini carbonyl clusters result in heterometallic Ni-Pt Chini-type clusters of the general formula [Pt6-xNix(CO)12]2- (x = 0-6). Their molecular structures have been determined by single-crystal X-ray diffraction (SC-XRD), showing a common octahedral (staggered, D3d) structure analogous to that of [Ni6(CO)12]2-, whereas [Pt6(CO)12]2- displays a trigonal-prismatic (eclipsed, D3h) structure. This structural change after replacing one single Pt with Ni may be classified as an alloying effect, and it has been theoretically investigated by DFT methods. Spectroscopic (IR and 195Pt and 13C NMR) and ESI-MS studies indicate that mixtures of [Pt6-xNix(CO)12]2- (x = 0-6) clusters are actually present in solution, whose compositions may be varied in an almost continuous way. Thus, they may be viewed as random alloy clusters whose overall compositions depend on the stoichiometry of the reagents.

Cesari C., Berti B., Bortoluzzi M., Femoni C., Iapalucci M.C., Zacchini S. (2021). Heterometallic Ni-Pt Chini-Type Carbonyl Clusters: An Example of Molecular Random Alloy Clusters. INORGANIC CHEMISTRY, 60(12), 8811-8825 [10.1021/acs.inorgchem.1c00752].

Heterometallic Ni-Pt Chini-Type Carbonyl Clusters: An Example of Molecular Random Alloy Clusters

Cesari C.;Berti B.;Femoni C.;Iapalucci M. C.;Zacchini S.
2021

Abstract

The direct reactions of homometallic [Ni6(CO)12]2- and [Pt6(CO)12]2- Chini carbonyl clusters result in heterometallic Ni-Pt Chini-type clusters of the general formula [Pt6-xNix(CO)12]2- (x = 0-6). Their molecular structures have been determined by single-crystal X-ray diffraction (SC-XRD), showing a common octahedral (staggered, D3d) structure analogous to that of [Ni6(CO)12]2-, whereas [Pt6(CO)12]2- displays a trigonal-prismatic (eclipsed, D3h) structure. This structural change after replacing one single Pt with Ni may be classified as an alloying effect, and it has been theoretically investigated by DFT methods. Spectroscopic (IR and 195Pt and 13C NMR) and ESI-MS studies indicate that mixtures of [Pt6-xNix(CO)12]2- (x = 0-6) clusters are actually present in solution, whose compositions may be varied in an almost continuous way. Thus, they may be viewed as random alloy clusters whose overall compositions depend on the stoichiometry of the reagents.
2021
Cesari C., Berti B., Bortoluzzi M., Femoni C., Iapalucci M.C., Zacchini S. (2021). Heterometallic Ni-Pt Chini-Type Carbonyl Clusters: An Example of Molecular Random Alloy Clusters. INORGANIC CHEMISTRY, 60(12), 8811-8825 [10.1021/acs.inorgchem.1c00752].
Cesari C.; Berti B.; Bortoluzzi M.; Femoni C.; Iapalucci M.C.; Zacchini S.
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11585/830149
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