Issue 21, 2024

Metal–ring interactions in group 2 ansa-metallocenes: assessed with the local vibrational mode theory

Abstract

Ansa-metallocenes, a vital class of organometallic compounds, have attracted significant attention due to their diverse structural motifs and their pivotal roles in catalysis and materials science. We investigated 37 distinct group 2 ansa-metallocenes at the B3LYP-D3/def2-TZVP level of theory. Utilizing local mode force constants derived from our local vibrational mode theory, including a special force constant directly targeting the metal–ring interaction, we could unveil latent structural differences between solvated and non-solvated metallocenophanes and the influence of the solvent on complex stability and structure. We could quantify the intrinsic strength of the metal–cyclopentadienyl (M–Cp) bonds and the influence of the bridging motifs on the stiffness of the Cp–M–Cp angles, another determinant of complex stability. LMA was complemented by the analysis of electronic density, utilizing the quantum theory of atoms in molecules (QTAIM), which confirmed both the impact of solvent coordination on the strength of the M–Cp bond(s) and the influence of the bridging motif on the Cp–M–Cp angles. The specific effect of the ansa-motif on the M–Cp interaction was further elucidated by a comparison with linear/bent metallocene structures. In summary, our results identify the local mode analysis as an efficient tool for unraveling the intricate molecular properties of ansa-metallocenes and their unique structural features.

Graphical abstract: Metal–ring interactions in group 2 ansa-metallocenes: assessed with the local vibrational mode theory

Supplementary files

Article information

Article type
Paper
Submitted
18 Jan 2024
Accepted
12 Apr 2024
First published
22 Apr 2024

Phys. Chem. Chem. Phys., 2024,26, 15143-15155

Metal–ring interactions in group 2 ansa-metallocenes: assessed with the local vibrational mode theory

J. J. Antonio and E. Kraka, Phys. Chem. Chem. Phys., 2024, 26, 15143 DOI: 10.1039/D4CP00225C

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements