Structural and Bonding Analyses on a Homologous Metal-Metal Bond Guest-Host Series M2@C50X10 (M = Zn, Cd, Hg; X = CH, N, B)

A systematic density functional study was performed on the structures and bonding features in a homologous metal–metal (M–M) host–guest series M2@C50X10 (M = Zn, Cd, Hg; X = CH, N, B). Calculations indicated that D5d conformers are energy minima for Zn2@C50X10 (X = CH, N) and Cd2@C50X10 (X = CH, N,...

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Bibliographic Details
Published in:European journal of inorganic chemistry 2013-04, Vol.2013 (12), p.2220-2230
Main Authors: Liu, Yan-Chun, Wu, Shui-Xing, Kan, Yu-He, Zhang, Hou-Yu, Su, Zhong-Min
Format: Article
Language:English
Subjects:
Density functional calculations
Fullerenes
Host-guest systems
Metal-metal interactions
Metallocenes
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Summary:A systematic density functional study was performed on the structures and bonding features in a homologous metal–metal (M–M) host–guest series M2@C50X10 (M = Zn, Cd, Hg; X = CH, N, B). Calculations indicated that D5d conformers are energy minima for Zn2@C50X10 (X = CH, N) and Cd2@C50X10 (X = CH, N, B), whereas Zn2@C50B10 has no imaginary frequency with the lowered C2h symmetry. Among these hybrid fullerene–metal complexes, those with dizinc and dicadmium guests adopt η5/η5 coordination, except for an η2/η2 case in C2h‐Zn2@C50B10, to meet appropriate interactions between the metal atom and cage; and the η1/η1 coordination mode can only be satisfied in just one (Hg2@C50N10) of the complexes with Hg–Hg guests, regardless of the enforced coordination surroundings. The nature of metal–cage interactions between M22+ and C50X102– moieties and M–M bonds have been analyzed by means of the topological properties of electron densities and energy‐partitioning methods, and results suggest that the two types of interactions are almost similar to those in their M2(C5H5)2 counterparts. Metal–metal bonds that consist of Group 12 elements were computationally introduced into three types of hybrid fullerene cages. The structures, stabilities, and bonding situations of these M2@C50X10 (M = Zn, Cd, Hg; X = CH, N, B) complexes were analyzed.
ISSN:1434-1948
1099-0682
DOI:10.1002/ejic.201201416