Revisiting the origin of the bending in group 2 metallocenes AeCp 2 (Ae = Be–Ba)
2023 | journal article. A publication with affiliation to the University of Göttingen.
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Revisiting the origin of the bending in group 2 metallocenes AeCp 2 (Ae = Be–Ba)
Sergeieva, T.; Demirer, T. I.; Wuttke, A.; Mata, R. A.; Schäfer, A.; Linker, G.-J. & Andrada, D. M. (2023)
Physical Chemistry, Chemical Physics, 25(30) pp. 20657-20667. DOI: https://doi.org/10.1039/D2CP05020J
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Details
- Authors
- Sergeieva, Tetiana; Demirer, T. Ilgin; Wuttke, Axel; Mata, Ricardo A.; Schäfer, André; Linker, Gerrit-Jan; Andrada, Diego M.
- Abstract
- Metallocenes are well-established compounds in organometallic chemistry, which can exhibit either a coplanar structure or a bent structure according to the nature of the metal center (E) and cyclopentadienyl ligands (Cp).
Metallocenes are well-established compounds in organometallic chemistry, and can exhibit either a coplanar structure or a bent structure according to the nature of the metal center (E) and the cyclopentadienyl ligands (Cp). Herein, we re-examine the chemical bonding to underline the origins of the geometry and stability observed experimentally. To this end, we have analysed a series of group 2 metallocenes [Ae(C 5 R 5 ) 2 ] (Ae = Be–Ba and R = H, Me, F, Cl, Br, and I) with a combination of computational methods, namely energy decomposition analysis (EDA), polarizability model (PM), and dispersion interaction densities (DIDs). Although the metal–ligand bonding nature is mainly an electrostatic interaction (65–78%), the covalent character is not negligible (33–22%). Notably, the heavier the metal center, the stronger the d-orbital interaction with a 50% contribution to the total covalent interaction. The dispersion interaction between the Cp ligands counts only for 1% of the interaction. Despite that orbital contributions become stronger for heavier metals, they never represent the energy main term. Instead, given the electrostatic nature of the metallocene bonds, we propose a model based on polarizability, which faithfully predicts the bending angle. Although dispersion interactions have a fair contribution to strengthen the bending angle, the polarizability plays a major role. - Issue Date
- 2023
- Journal
- Physical Chemistry, Chemical Physics
- ISSN
- 1463-9076
- eISSN
- 1463-9084
- Language
- English
- Sponsor
- European Research Council https://doi.org/10.13039/501100000781
Deutsche Forschungsgemeinschaft https://doi.org/10.13039/501100001659