The anionic cluster [Pt19(CO)22]4– (1), of pentagonal symmetry, reacts with CO and AuPPh3+ fragments. Upon increasing the Au:Pt19 molar ratio, different species are sequentially formed, but only the last two members of the series could be characterized by X-ray diffraction, namely, [Pt19(CO)24(μ4-AuPPh3)3]− (2) and [Pt19(CO)24{μ4-Au2(PPh3)2}2] (3). The metallic framework of the starting cluster is completely modified after the addition of CO and AuL+, and both products display the same platinum core of trigonal symmetry, with closely packed metal atoms. The three AuL+ units cap three different square faces in 2, whereas four AuL+ fragments are grouped in two independent bimetallic units in the neutral cluster 3. Electrochemical and spectroelectrochemical studies on 2 showed that its redox ability is comparable with that of the homometallic 1.
Ceriotti, A., Macchi, P., Sironi, A., El Afefey, S., Daghetta, M., Fedi, S., et al. (2013). Cooperative Effects of Electron Donors and Acceptors for the Stabilization of Elusive Metal Cluster Frameworks: Synthesis and Solid-State Structures of [Pt19(CO)24(μ4‑AuPPh3)3]− and [Pt19(CO)24{μ4‑Au2(PPh3)2}2]. INORGANIC CHEMISTRY, 52(4), 1960-1964 [10.1021/ic302282y].
Cooperative Effects of Electron Donors and Acceptors for the Stabilization of Elusive Metal Cluster Frameworks: Synthesis and Solid-State Structures of [Pt19(CO)24(μ4‑AuPPh3)3]− and [Pt19(CO)24{μ4‑Au2(PPh3)2}2]
SIRONI, ANNALISA;DELLA PERGOLA, ROBERTO
2013
Abstract
The anionic cluster [Pt19(CO)22]4– (1), of pentagonal symmetry, reacts with CO and AuPPh3+ fragments. Upon increasing the Au:Pt19 molar ratio, different species are sequentially formed, but only the last two members of the series could be characterized by X-ray diffraction, namely, [Pt19(CO)24(μ4-AuPPh3)3]− (2) and [Pt19(CO)24{μ4-Au2(PPh3)2}2] (3). The metallic framework of the starting cluster is completely modified after the addition of CO and AuL+, and both products display the same platinum core of trigonal symmetry, with closely packed metal atoms. The three AuL+ units cap three different square faces in 2, whereas four AuL+ fragments are grouped in two independent bimetallic units in the neutral cluster 3. Electrochemical and spectroelectrochemical studies on 2 showed that its redox ability is comparable with that of the homometallic 1.
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