This paper reports a detailed study of the oxidation and reduction reactions of simple nickel mono-carbide and mono-acetlyde carbonyl clusters. The reduction of [Ni9C(CO)17]2–with Na/naphtalene affords the new [Ni12C(CO)18]4–mono-carbide cluster. Under the same experimental conditions, [Ni10(C2)(CO)16]2–reacts with Na/naphtalene yielding a mixture of the previously reported [Ni11(C2)(CO)15]4–and [Ni12(C2)(CO)16]4–mono-acetylide tetra-anions. The oxidation reactions of both [Ni9C(CO)17]2–and [Ni10(C2)(CO)16]2–, carried out with miscellaneous reagents, e.g., [C7H7][BF4], [Cp2Fe][PF6], AgNO3, are more complicated and less selective, leading to mixtures of products, among which the previously reported [Ni8C(CO)16]2–, [Ni16(C2)2(CO)23]4–, [Ni38C6(CO)42]6–and [Ni32C6(CO)36]6–species have been identified. Interestingly, oxidation of [Ni10(C2)(CO)16]2–with Pd(Et2S)2Cl2affords the new tetra-acetylide [Ni22(C2)4(CO)28(Et2S)]2–, even if in low yields. The new species [Ni12C(CO)18]4–and [Ni22(C2)4(CO)28(Et2S)]2–have been structurally characterized by means of single crystal X-ray diffraction. Electrochemical and spectroelectrochemical studies have been performed on [Ni12C(CO)18]4–. This compound can be electrochemically oxidized and reduced reversibly affording [Ni12C(CO)18]3–and [Ni12C(CO)18]5–, respectively. The same species can be obtained by chemical methods but, due to their limited stability during work-up, it has not been possible to isolate them.

Ciabatti, I., Femoni, C., Funaioli, T., Iapalucci, M.C., Merighi, S., Zacchini, S. (2017). The redox chemistry of [Ni9C(CO)17]2â and [Ni10(C2)(CO)16]2â : Synthesis, electrochemistry and structure of [Ni12C(CO)18]4â and [Ni22(C2)4(CO)28(Et2S)]2â . JOURNAL OF ORGANOMETALLIC CHEMISTRY, 849-850, 299-305 [10.1016/j.jorganchem.2017.01.029].

The redox chemistry of [Ni9C(CO)17]2–and [Ni10(C2)(CO)16]2–: Synthesis, electrochemistry and structure of [Ni12C(CO)18]4–and [Ni22(C2)4(CO)28(Et2S)]2–

Ciabatti, Iacopo;Femoni, Cristina;Iapalucci, Maria Carmela;Merighi, Stefano;Zacchini, Stefano
2017

Abstract

This paper reports a detailed study of the oxidation and reduction reactions of simple nickel mono-carbide and mono-acetlyde carbonyl clusters. The reduction of [Ni9C(CO)17]2–with Na/naphtalene affords the new [Ni12C(CO)18]4–mono-carbide cluster. Under the same experimental conditions, [Ni10(C2)(CO)16]2–reacts with Na/naphtalene yielding a mixture of the previously reported [Ni11(C2)(CO)15]4–and [Ni12(C2)(CO)16]4–mono-acetylide tetra-anions. The oxidation reactions of both [Ni9C(CO)17]2–and [Ni10(C2)(CO)16]2–, carried out with miscellaneous reagents, e.g., [C7H7][BF4], [Cp2Fe][PF6], AgNO3, are more complicated and less selective, leading to mixtures of products, among which the previously reported [Ni8C(CO)16]2–, [Ni16(C2)2(CO)23]4–, [Ni38C6(CO)42]6–and [Ni32C6(CO)36]6–species have been identified. Interestingly, oxidation of [Ni10(C2)(CO)16]2–with Pd(Et2S)2Cl2affords the new tetra-acetylide [Ni22(C2)4(CO)28(Et2S)]2–, even if in low yields. The new species [Ni12C(CO)18]4–and [Ni22(C2)4(CO)28(Et2S)]2–have been structurally characterized by means of single crystal X-ray diffraction. Electrochemical and spectroelectrochemical studies have been performed on [Ni12C(CO)18]4–. This compound can be electrochemically oxidized and reduced reversibly affording [Ni12C(CO)18]3–and [Ni12C(CO)18]5–, respectively. The same species can be obtained by chemical methods but, due to their limited stability during work-up, it has not been possible to isolate them.
2017
Ciabatti, I., Femoni, C., Funaioli, T., Iapalucci, M.C., Merighi, S., Zacchini, S. (2017). The redox chemistry of [Ni9C(CO)17]2â and [Ni10(C2)(CO)16]2â : Synthesis, electrochemistry and structure of [Ni12C(CO)18]4â and [Ni22(C2)4(CO)28(Et2S)]2â . JOURNAL OF ORGANOMETALLIC CHEMISTRY, 849-850, 299-305 [10.1016/j.jorganchem.2017.01.029].
Ciabatti, Iacopo; Femoni, Cristina; Funaioli, Tiziana; Iapalucci, Maria Carmela; Merighi, Stefano; Zacchini, Stefano
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11585/613482
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