The oxidation of [Ph3P(CH2)12PPh3][Pt15(CO)30] with CF3COOH in THF afforded [Ph3P(CH2)12PPh3][Pt18(CO)36] as a precipitate which was re-crystallized from dmf/iso-propanol. This salt self-assembles in the solid state adopting an unprecedented morphology which consists of infinite chains of [Pt9(CO)18]– units. The solid state structure of [Ph3P(CH2)12PPh3][Pt18(CO)36] may be viewed as a snapshot in which [Pt9(CO)18]– units are approaching and ready to exchange outer Pt3(CO)6 fragments. The reactions of Chini clusters with isonitriles proceed via redox-fragmentation, at difference with those involving phosphines that may occur both via non-redox substitution and redox fragmentation, depending on the experimental conditions. Thus, the reaction of [Pt6(CO)12]2– with CNXyl afforded Pt5(CNXyl)10, whereas Pt9(CNXyl)13(CO) was obtained from the reaction of [Pt15(CO)30]2– with CNXyl. These two new neutral clusters have been structurally characterized as their Pt5(CNXyl)10·2toluene and Pt9(CNXyl)13(CO)·solv solvates. DFT studies on the CO exchange of [Pt6(CO)12]2– suggest an associative interchange mechanism, which may be extended also to larger Chini clusters and the initial steps of their reactions with other soft nucleophiles.

Further insights into platinum carbonyl Chini clusters

Berti, Beatrice;Cesari, Cristiana;Femoni, Cristina;Carmela Iapalucci, Maria;Zacchini, Stefano
2020

Abstract

The oxidation of [Ph3P(CH2)12PPh3][Pt15(CO)30] with CF3COOH in THF afforded [Ph3P(CH2)12PPh3][Pt18(CO)36] as a precipitate which was re-crystallized from dmf/iso-propanol. This salt self-assembles in the solid state adopting an unprecedented morphology which consists of infinite chains of [Pt9(CO)18]– units. The solid state structure of [Ph3P(CH2)12PPh3][Pt18(CO)36] may be viewed as a snapshot in which [Pt9(CO)18]– units are approaching and ready to exchange outer Pt3(CO)6 fragments. The reactions of Chini clusters with isonitriles proceed via redox-fragmentation, at difference with those involving phosphines that may occur both via non-redox substitution and redox fragmentation, depending on the experimental conditions. Thus, the reaction of [Pt6(CO)12]2– with CNXyl afforded Pt5(CNXyl)10, whereas Pt9(CNXyl)13(CO) was obtained from the reaction of [Pt15(CO)30]2– with CNXyl. These two new neutral clusters have been structurally characterized as their Pt5(CNXyl)10·2toluene and Pt9(CNXyl)13(CO)·solv solvates. DFT studies on the CO exchange of [Pt6(CO)12]2– suggest an associative interchange mechanism, which may be extended also to larger Chini clusters and the initial steps of their reactions with other soft nucleophiles.
Berti, Beatrice; Bortoluzzi, Marco; Ceriotti, Alessandro; Cesari, Cristiana; Femoni, Cristina; Carmela Iapalucci, Maria; Zacchini, Stefano
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11585/782538
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