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Theoretical studies on all-metal binuclear sandwich-like complexes M2(η4-E4)2 (M=Al, Ga, In; E=Sb, Bi)

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Abstract

A series of all-metal binuclear sandwich-like complexes with the formula M2(η4-E4)2 (M=Al, Ga, In; E=Sb, Bi) was studied by density functional theory (DFT). The most stable conformer for each of the M2(η4-E4)2 species is the staggered one with D 4d symmetry. The centred metal–metal bond in each M2(η4-E4)2 species is a covalent single bond, with the main contributors to these covalent bonds being the a1 and e orbitals. For all these species, the interactions between the centred metal atoms and the all-metal ligands are covalent; η4-Sb 2−4 has a stronger ability to stabilize metal–metal bonds than η4-Bi 2−4 . Nucleus-independent chemical shifts (NICS) values and molecular orbital (MO) analysis reveal that the all-metal η4-Sb 2-4 and η4-Bi 2-4 ligands in M2(η4-E4)2 possess conflicting aromaticity (σ antiaromaticity and π aromaticity), which differs from the all-metal multiple aromatic unit Al 2−4 . In addition, all of these M2(η4-E4)2 species are stable according to the dissociation energies of M2(η4-E4)2 → 2 M(η4-E4) and M2(η4-E4)2 → 2 M + 2E4, and these stable species can be synthesized by two-step substitution reactions: CpZnZnCp + 2E 2−4  → [E4ZnZnE4]2− + 2Cp− and [E4ZnZnE4]2− + 2 M +2  → E4MME4 + 2Zn+.

Molecular structures for M2(η4-E4)2(M=Al, Ga, In; E=Sb, Bi)

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Acknowledgments

We are indebted to the Chinese National Natural Science Foundation (20903010), Research Fund for the Doctoral Program of Higher Education (200800071019), and Project of State Key Laboratory of Explosion Science of Technology (Beijing Institute of Technology) (2DkT10-01a).

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Authors and Affiliations

  1. Institute of Chemical Physics, Beijing Institute of Technology, Beijing, 100081, People’s Republic of China

    Congzhi Wang, Xiuhui Zhang, Jian Lu & Qianshu Li

  2. Center for Computational Quantum Chemistry, South China Normal University, Guangzhou, 510631, People’s Republic of China

    Qianshu Li

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  1. Congzhi Wang
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  2. Xiuhui Zhang
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Correspondence to Xiuhui Zhang or Qianshu Li.

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Wang, C., Zhang, X., Lu, J. et al. Theoretical studies on all-metal binuclear sandwich-like complexes M2(η4-E4)2 (M=Al, Ga, In; E=Sb, Bi). J Mol Model 18, 3577–3586 (2012). https://doi.org/10.1007/s00894-012-1362-y

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