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Symmetry Reduction upon Size Mismatch: The Non‐Icosahedral Intermetalloid Cluster [Co@Ge 12 ] 3−
Author(s) -
Liu Chao,
Li LeiJiao,
Popov Ivan A.,
Wilson Robert J.,
Xu CongQiao,
Li Jun,
Boldyrev Alexander I.,
Sun ZhongMing
Publication year - 2018
Publication title -
chinese journal of chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.28
H-Index - 41
eISSN - 1614-7065
pISSN - 1001-604X
DOI - 10.1002/cjoc.201800434
Subject(s) - icosahedral symmetry , chemistry , cluster (spacecraft) , crystallography , covalent bond , ethylenediamine , metal , germanium , symmetry (geometry) , geometry , inorganic chemistry , silicon , mathematics , organic chemistry , computer science , programming language
A new complex comprising [Co@Ge 12 ] 3– cluster core was synthesized through the reaction of CoMe(PMe 3 ) 4 and K 4 Ge 9 in ethylenediamine solution. The pseudo‐ D 5d geometry of this cluster can be viewed as structurally derived from an icosahedral cage via Jahn‐Teller effect, leading to notable bonding differences from I h ‐[M@E 12 ] q − clusters (E = Sn, Pb with q = 2, 3). The [Co@Ge 12 ] 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@Ge 12 ] 3− (M = Rh, Ir, Mt) indicate that similar compounds of larger‐size metal atoms can drive the complete transformation of [M@Ge 12 ] 3− clusters from icosahedron structure to a sandwich one.