Cobalt-Centered Ten-Vertex Germanium Clusters: The Pentagonal Prism as an Alternative to Polyhedra Predicted by the Wade–Mingos Rules

One of the most exciting recent (2009) discoveries in metal cluster chemistry is the pentagonal prismatic Co@Ge10 3– ion, found in [K­(2,2,2-crypt)]4[Co@Ge10]­[Co­(1,5-C8H12)2]·toluene and characterized structurally by X-ray diffraction. The complete absence of triangular faces in the pentagonal pri...

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Published in:Inorganic chemistry 2012-03, Vol.51 (6), p.3498-3504
Main Authors: Uţă, M. M, Cioloboc, D, King, R. B
Format: Article
Language:English
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Summary:One of the most exciting recent (2009) discoveries in metal cluster chemistry is the pentagonal prismatic Co@Ge10 3– ion, found in [K­(2,2,2-crypt)]4[Co@Ge10]­[Co­(1,5-C8H12)2]·toluene and characterized structurally by X-ray diffraction. The complete absence of triangular faces in the pentagonal prismatic structure of Co@Ge10 3– contradicts expectations from the well-established Wade–Mingos rules, which predict polyhedral structures having mainly or entirely triangular faces. A theoretical study on Co@Ge10 z systems (z = −5 to +1) predicts a singlet D 5h pentagonal prismatic global minimum for the trianion Co@Ge10 3– in accord with this experimental result. Redox reactions on this pentagonal prismatic Co@Ge10 3– trianion generate low-energy pentagonal prismatic structures for Co@Ge10 z where z = 0, −1, −2, −4, and −5 having quartet, triplet, doublet, doublet, and triplet spin states, respectively. Similar theoretical methods predict a singlet C 3v polyhedral structure for the monoanion Co@Ge10 –, similar to previous theoretical predictions on the isoelectronic neutral Ni@Ge10 and the structure realized experimentally in the isoelectronic Ni@In10 10– found in the K10In10Ni intermetallic. Redox reactions on this C 3v polyhedral Co@Ge10 – monoanion generate low energy C 3v polyhedral structures for Co@Ge10 z where z = 0, −2, −3, and −4 having doublet, doublet, triplet, and quartet spin states, respectively.
ISSN:0020-1669
1520-510X
DOI:10.1021/ic202226k