TY - JOUR
T1 - The electronic structures and aromaticities for zinc sandwich, half-sandwich and zinc-zinc (Zn22+) sandwich complexes within density functional theory
AU - Liu, Zi Zhong
AU - Tian, Wei Quan
AU - Feng, Ji Kang
AU - Zhang, Gang
AU - Li, Wei Qi
N1 - Funding Information:
This research was supported by the National Nature Science Foundation of China (No. 20473031) and the Key Laboratory for Supramolecular Structure and Material of Jilin University. WQT thanks Japan Society for the Promotion of Science for financial support and is grateful to Professor Yuriko Aoki for her hospitality.
PY - 2006/1/31
Y1 - 2006/1/31
N2 - The equilibrium geometries, energies, harmonic frequencies, and nucleus-independent chemical shifts of the zinc sandwich, the half-sandwich, and the zinc-zinc (Zn22+) sandwich complexes are computed by B3LYP/6-311++G(d,p) within the density functional theory. The staggered [(η5-C5H5)2Zn2] (1A1, D5d) is the most stable minimum with higher binding energy and slightly stronger aromaticity than those of the η5-C5H5- (1A 1, D5h). The eclipsed [(η5-C 5H5)2Zn2] (1A 1, D5h) is a transition state with a small ring rotation barrier. The Zn-containing half-sandwich complexes are minima while with different stabilities and aromaticity. Particularly, the [(η5- C5H5)Zn] (2A1, C5v) has larger binding energy with aromaticity slightly weaker than η5- C5H5-, this compound features a simple while bona fide monovalent zinc molecular compound. The Zn2+ sandwich complex, [Zn(η5-C5H5)2] ( 1A1, D5h and D5d), with aromaticity weaker than that of the slip-sandwich complex, is a saddle point on potential energy surface. The slip-sandwich complex, (η1-C 5H5)Zn(η5-C5H5) (1A1, C1), with aromaticity close to that of η5-C5H5- (1A 1, D5h), is a local minimum. Both the eclipsed and the staggered [(C5(CH3)5)2Zn 2](C1) are aromatic with aromaticity close to that of [(η5-C5H5)2Zn2] (D5d). According to the analysis of molecular orbitals, the Wiberg bond indices, the magnitude of charge transfer, the total nucleus-independent chemical shifts distributions, and the nucleus-independent chemical shifts contribution distributions of various bonds manifests, the stabilities of all the Zn-containing sandwich, the half-sandwich, and the Zn2 2+ sandwich complexes are accredited to both ionic electrostatic interactions and covalent binding, especially the ionic electrostatic interactions, between the metal center and the η5-C 5H5- building blocks.
AB - The equilibrium geometries, energies, harmonic frequencies, and nucleus-independent chemical shifts of the zinc sandwich, the half-sandwich, and the zinc-zinc (Zn22+) sandwich complexes are computed by B3LYP/6-311++G(d,p) within the density functional theory. The staggered [(η5-C5H5)2Zn2] (1A1, D5d) is the most stable minimum with higher binding energy and slightly stronger aromaticity than those of the η5-C5H5- (1A 1, D5h). The eclipsed [(η5-C 5H5)2Zn2] (1A 1, D5h) is a transition state with a small ring rotation barrier. The Zn-containing half-sandwich complexes are minima while with different stabilities and aromaticity. Particularly, the [(η5- C5H5)Zn] (2A1, C5v) has larger binding energy with aromaticity slightly weaker than η5- C5H5-, this compound features a simple while bona fide monovalent zinc molecular compound. The Zn2+ sandwich complex, [Zn(η5-C5H5)2] ( 1A1, D5h and D5d), with aromaticity weaker than that of the slip-sandwich complex, is a saddle point on potential energy surface. The slip-sandwich complex, (η1-C 5H5)Zn(η5-C5H5) (1A1, C1), with aromaticity close to that of η5-C5H5- (1A 1, D5h), is a local minimum. Both the eclipsed and the staggered [(C5(CH3)5)2Zn 2](C1) are aromatic with aromaticity close to that of [(η5-C5H5)2Zn2] (D5d). According to the analysis of molecular orbitals, the Wiberg bond indices, the magnitude of charge transfer, the total nucleus-independent chemical shifts distributions, and the nucleus-independent chemical shifts contribution distributions of various bonds manifests, the stabilities of all the Zn-containing sandwich, the half-sandwich, and the Zn2 2+ sandwich complexes are accredited to both ionic electrostatic interactions and covalent binding, especially the ionic electrostatic interactions, between the metal center and the η5-C 5H5- building blocks.
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U2 - 10.1016/j.theochem.2005.10.025
DO - 10.1016/j.theochem.2005.10.025
M3 - Article
AN - SCOPUS:32144448902
VL - 758
SP - 127
EP - 138
JO - Computational and Theoretical Chemistry
JF - Computational and Theoretical Chemistry
SN - 2210-271X
IS - 2-3
ER -