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Icosahedral Ga‐Centred Nickel Carbonyl Clusters: Synthesis and Characterization of [H 3– n Ni 12 (μ 12 ‐Ga)(CO) 22 ] n– ( n = 2, 3) and [Ni 14.3 (μ 12 ‐Ga)(CO) 24.3 ] 3– Anions
Author(s) -
Femoni Cristina,
Iapalucci Maria Carmela,
Longoni Giuliano,
Zacchini Stefano
Publication year - 2010
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200900904
Subject(s) - chemistry , carbon monoxide , icosahedral symmetry , nickel , hydride , crystallography , cluster (spacecraft) , inorganic chemistry , borane , crystallization , protonation , hydrogen , catalysis , organic chemistry , computer science , programming language , ion
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.