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Stability and donor-acceptor bond in dinuclear organometallics CpM1–M2Cl3 (M1, M2 = B, Al, Ga, In; Cp = η 5–C5H5)

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Abstract

The geometries and stabilities of the dinuclear organometallics CpM1–M2Cl3 (M1, M2 = B, Al, Ga, In; Cp = η 5-C5H5) have been investigated by density functional theory (DFT) at M06 L/6-311G(d, p) levels. The nature of the donor–acceptor M1 → M2 bond was also studied based on the atoms in molecules (AIM) theory, energy decomposition analysis (EDA) and natural bond orbital (NBO) analysis. The results show that the electronegativity of the M atom determines the stability and covalent character of the dinuclear organometallics CpM1–M2Cl3. The compounds in which the M with larger electronegativity acts as the donor are more stable than in those in which it acts as the acceptor in the donor–acceptor bond, and the donor–acceptor bond has more covalent characteristics. The strength and polarity of the M1 → M2 donor–acceptor bond is determined by the periodicity of the M atom. When the period number of the M1 atom is smaller than that of M2, the strength of the M1 → M2 bond is larger than that of the M2 → M1 bond. For homonuclear dinuclear organometallics, the polarity of the M–M bond increases with increasing atomic number of the M atom. For heteronuclear complexes, the polarity of the M1–M2 bond for a given M1 also increases in the sequence of M2 = B, Al, Ga, and In.

Molecular graph and electron location function isosurfaces map of CpM 1 –M 2 Cl 3(small red spheres represent bond critical points)

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Acknowledgments

Thanks to Elsevier Language Editing Services for editing this paper. This work was supported by the National Natural Science Foundation of China (NSFC; contract nos. 21372062, 21373075), the Natural Science Foundation of Hebei Province (contract no. B2016205042).

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Authors and Affiliations

  1. College of Chemistry and Material Science, Hebei Normal University, Road East of 2nd Ring South, Shijiazhuang, 050024, China

    Yaru Dang, Lingpeng Meng, Mei Qin & Xiaoyan Li

  2. Key Laboratory of Inorganic Nano-materials of Hebei Province, Shijiazhuang, 050024, China

    Lingpeng Meng & Xiaoyan Li

  3. The Laboratory of Theoretical and Computational Chemistry, Science and Engineering College of Chemistry and Biology, Yantai University, Yantai, 264005, China

    Qingzhong Li

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Dang, Y., Meng, L., Qin, M. et al. Stability and donor-acceptor bond in dinuclear organometallics CpM1–M2Cl3 (M1, M2 = B, Al, Ga, In; Cp = η 5–C5H5). J Mol Model 24, 7 (2018). https://doi.org/10.1007/s00894-017-3539-x

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