TY - JOUR
T1 - Which kind of binuclear sandwich-like compound is more stable in M 2(η 4-E 4) 2 (M=B, Al, Ga; E=XYZ=BCO, BNN, CBO), the metal centered or the non-metal centered sandwich-like complex?
AU - Peng, Aiping
AU - Zhang, Xiuhui
AU - Li, Qianshu
AU - Hu, Haixiang
AU - Ji, Lin
PY - 2012/9/15
Y1 - 2012/9/15
N2 - To investigate the difference between the non-metal centered and metal centered binuclear sandwich-like compounds, a series of novel non-metal centered and metal centered binuclear sandwich-like complexes M 2(η 4-E 4) 2 (M=B, Al, Ga; E=XYZ=BCO, BNN, CBO) have been studied by the density functional theory (DFT). The bonding characters of each species are discussed by the natural bond orbital (NBO), atoms in molecules (AIM) and molecular orbitals (MO) analysis. The aromaticity of the stable structures is analysized by the criterion of the nucleus-independent chemical shifts (NICS). The thermodynamic stabilities of M 2(η 4-E 4) 2 are investigated by the dissociation reactions and isomerization reactions. It is found that the E42- rings as the ligands can form the stable binuclear sandwich-like complexes, and the synthesis of M 2(η 4-E 4) 2 in future is desirable. Moreover, the non-metal centered sandwich-like compounds are more stable than the metal centered ones and the CBO-based compounds are energetically favored than their BCO-based isomers. The main difference of the bonding nature between the non-metal centered and metal centered binuclear sandwich-like complex is the interaction between the centered atoms and the ligands: one is predominantly covalent and the other is mainly ionic.
AB - To investigate the difference between the non-metal centered and metal centered binuclear sandwich-like compounds, a series of novel non-metal centered and metal centered binuclear sandwich-like complexes M 2(η 4-E 4) 2 (M=B, Al, Ga; E=XYZ=BCO, BNN, CBO) have been studied by the density functional theory (DFT). The bonding characters of each species are discussed by the natural bond orbital (NBO), atoms in molecules (AIM) and molecular orbitals (MO) analysis. The aromaticity of the stable structures is analysized by the criterion of the nucleus-independent chemical shifts (NICS). The thermodynamic stabilities of M 2(η 4-E 4) 2 are investigated by the dissociation reactions and isomerization reactions. It is found that the E42- rings as the ligands can form the stable binuclear sandwich-like complexes, and the synthesis of M 2(η 4-E 4) 2 in future is desirable. Moreover, the non-metal centered sandwich-like compounds are more stable than the metal centered ones and the CBO-based compounds are energetically favored than their BCO-based isomers. The main difference of the bonding nature between the non-metal centered and metal centered binuclear sandwich-like complex is the interaction between the centered atoms and the ligands: one is predominantly covalent and the other is mainly ionic.
KW - Aromaticity
KW - Binuclear sandwich-like compounds
KW - Bonding characters
KW - Density functional theory
KW - Thermodynamic stability
UR - http://www.scopus.com/inward/record.url?scp=84865413773&partnerID=8YFLogxK
U2 - 10.1016/j.comptc.2012.07.010
DO - 10.1016/j.comptc.2012.07.010
M3 - Article
AN - SCOPUS:84865413773
SN - 2210-271X
VL - 996
SP - 37
EP - 43
JO - Computational and Theoretical Chemistry
JF - Computational and Theoretical Chemistry
ER -