Please use this identifier to cite or link to this item:
doi:10.22028/D291-41232
Title: | Revisiting the origin of the bending in group 2 metallocenes AeCp2 (Ae = Be–Ba) |
Author(s): | Sergeieva, Tetiana Demirer, T. Ilgin Wuttke, Axel Mata, Ricardo A. Schäfer, André Linker, Gerrit-Jan Andrada, Diego M. |
Language: | English |
Title: | Physical Chemistry Chemical Physics |
Volume: | 25 |
Issue: | 30 |
Pages: | 20657-20667 |
Publisher/Platform: | Royal Society of Chemistry |
Year of Publication: | 2023 |
DDC notations: | 500 Science |
Publikation type: | Journal Article |
Abstract: | 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(C5R5)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. |
DOI of the first publication: | 10.1039/D2CP05020J |
URL of the first publication: | https://doi.org/10.1039/D2CP05020J |
Link to this record: | urn:nbn:de:bsz:291--ds-412321 hdl:20.500.11880/36982 http://dx.doi.org/10.22028/D291-41232 |
ISSN: | 1463-9084 1463-9076 |
Date of registration: | 28-Nov-2023 |
Description of the related object: | Electronic supplementary information |
Related object: | https://www.rsc.org/suppdata/d2/cp/d2cp05020j/d2cp05020j1.pdf |
Faculty: | NT - Naturwissenschaftlich- Technische Fakultät |
Department: | NT - Chemie |
Professorship: | NT - Prof. Dr. Guido Kickelbick NT - Prof. Dr. David Scheschkewitz |
Collections: | SciDok - Der Wissenschaftsserver der Universität des Saarlandes |
Files for this record:
File | Description | Size | Format | |
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d2cp05020j.pdf | 1,86 MB | Adobe PDF | View/Open |
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