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- Title
Symmetry Reduction upon Size Mismatch: The Non‐Icosahedral Intermetalloid Cluster [Co@Ge<sub>12</sub>]<sup>3−</sup>.
- Authors
Liu, Chao; Li, Lei‐Jiao; Popov, Ivan A.; Wilson, Robert J.; Xu, Cong‐Qiao; Li, Jun; Boldyrev, Alexander I.; Sun, Zhong‐Ming
- Abstract
A new complex comprising [Co@Ge12]3– cluster core was synthesized through the reaction of CoMe(PMe3)4 and K4Ge9 in ethylenediamine solution. The pseudo‐D5d geometry of this cluster can be viewed as structurally derived from an icosahedral cage via Jahn‐Teller effect, leading to notable bonding differences from Ih‐[M@E12]q− clusters (E = Sn, Pb with q = 2, 3). The [Co@Ge12]3– cluster represents a structural conundrum. On the basis of the geometric considerations it could be viewed as a sandwich complex. However, chemical bonding analysis revealed that there is a direct covalent multicenter bonding between the two pentagons, thus indicating that the structure should be viewed as an elongated icosahedron. Further theoretical calculations on [M@Ge12]3− (M = Rh, Ir, Mt) indicate that similar compounds of larger‐size metal atoms can drive the complete transformation of [M@Ge12]3− clusters from icosahedron structure to a sandwich one. The pseudo‐D5d geometry of [Co@Ge12]3– can be viewed as structurally derived from an icosahedral cage via Jahn‐Teller effect, leading to notable bonding differences from Ih‐[M@E12]q− clusters (E = Sn, Pb with q = 2, 3).
- Subjects
ETHYLENEDIAMINE; JAHN-Teller effect; CHEMICAL bonds; ZINTL compounds; PENTAGONS
- Publication
Chinese Journal of Chemistry, 2018, Vol 36, Issue 12, p1165
- ISSN
1001-604X
- Publication type
Article
- DOI
10.1002/cjoc.201800434