Citation: QIU Yi-Xiang, WANG Shu-Guang. Electronic Structures of Group IB Metal-Ethylene Complexes [N{(Me)C(Ph)N}₂]M-C₂H₄ (M=Cu, Ag, Au)[J]. Acta Physico-Chimica Sinica, ;2012, 28(04): 811-817. doi: 10.3866/PKU.WHXB201202082 shu

Electronic Structures of Group IB Metal-Ethylene Complexes [N{(Me)C(Ph)N}₂]M-C₂H₄ (M=Cu, Ag, Au)

1.
School of Chemistry and Chemical Technology, Shanghai Jiao Tong University, Shanghai 200240, P. R. China

Received Date: 14 November 2011
Available Online: 8 February 2012
Fund Project: 国家自然科学基金(20973109)资助项目 (20973109)

The geometries, electronic structures, and bonding energies of coinage metal-ethylene complexes LM-C₂H₄ (L=[N{(Me)C(Ph)N}₂]; M=Cu, Ag, Au) were investigated by Hartree-Fock, Møller- Plesset perturbation (MP2), second-order approximate coupled-cluster (CC2), and density functional theory (DFT) methods. The MP2, CC2, and DFT methods performed well in reproducing the experimental geometric features of LM-C₂H₄. The bonding in LM-C₂H₄ can be described as a synergistic combination of σ-donor and π-acceptor interactions between the LM and C₂H₄ π-system. Both σ-donor and π-acceptor contributions increased the C＝C bond length and decreased the C＝C bond strength by removing electron density from the bonding π orbital and increasing electron density in the anti-bonding π* orbital, respectively. The results of natural population analysis and energy decomposition analysis show that the LM→C₂H₄ back-donation contribution to the LM-C₂H₄ bonding is higher than that of the C₂H₄→LM donation, but this order is reversed in the M⁺-C₂H₄ systems. Therefore, it is not appropriate to use M⁺-C₂H₄ as a computational model for electronic structures studies of LM-C₂H₄. The effects of changing the metal on the structural and electronic properties, such as C＝C bond length, charge populations of C₂H₄, and LM-C₂H₄ interactions, were large. Compared with LCu and LAg, LAu had the strongest ability to accept and donate electrons. Consequently, it showed the maximum reduction in the π orbital electron density and increase in the π* orbital density. Therefore, activation of the C＝C bond by LAu was more effective than by LCu and LAg. However, the effects of electron donating or withdrawing ability of the auxiliary ligands on the above properties were small.
- Metal-ethylene complex,
- Ab initio,
- Density functional theory,
- Electronic structure,
- Energy decomposition analysis
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Electronic Structures of Group IB Metal-Ethylene Complexes [N{(Me)C(Ph)N}2]M-C2H4 (M=Cu, Ag, Au)

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通讯作者: 陈斌, bchen63@163.com

Electronic Structures of Group IB Metal-Ethylene Complexes [N{(Me)C(Ph)N}₂]M-C₂H₄ (M=Cu, Ag, Au)