Icosahedral Ga-Centred Nickel Carbonyl Clusters: Synthesis and Characterization of [H3–nNi12 (μ12-Ga)(CO)22]n– (n = 2, 3) and [Ni14.3(μ12-Ga)(CO)24.3]3– Anions

✍ Scribed by Cristina Femoni; Maria Carmela Iapalucci; Giuliano Longoni; Stefano Zacchini

• Book ID: 102166251
• Publisher: John Wiley and Sons
• Year: 2010
• Tongue: English
• Weight: 311 KB
• Volume: 2010
• Category: Article
• ISSN: 1434-1948
• DOI: 10.1002/ejic.200900904

✦ Synopsis

Abstract

The reaction of [Ni~5~(CO)~12~]^2–^ or [Ni~6~(CO)~12~]^2–^ with GaCl~3~ in dichloromethane under a nitrogen atmosphere affords a mixture of [Ni~12+x~(μ~12~‐Ga)(CO)~22+x~]^3–^ (x = 0–3) clusters. Short exposure of the above mixture to a carbon monoxide atmosphere leads to the green icosahedral [Ni~12~(μ~12~‐Ga)(CO)~22~]^3–^ trianion, which was isolated and characterized as its [N__n__Bu~4~]^+^ salt. In contrast, crystallization of the above mixture in the presence of Ni(CO)~4~ enabled isolation of a cocrystallized mixture of [Ni~14~(μ~12~‐Ga)(CO)~24~]^3–^ (70 %) and [Ni~15~(μ~12~‐Ga)(CO)~25~]^3–^ (30 %). As inferable from its structure, the additional three Ni(CO) moieties condense onto interlayer faces of the icosahedron. Protonation of [Ni~12~(μ~12~‐Ga)(CO)~22~]^3–^ affords the corresponding [HNi~12~(μ~12~‐Ga)(CO)~22~]^2–^ hydride derivative, which was isolated in a pure state and fully characterized. All of the above compounds conform to the cluster‐borane analogy, by the inclusion principle, and none exhibits relevant redox behaviour.