University of Illinois Urbana-Champaign

Wetting Ferrocene As A Way To Investigate Its Gas Phase Structure By Rotational Spectroscopy

Blanco, Susana

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MI03_1.pptx
5954.pdf

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https://hdl.handle.net/2142/116977

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Title
Wetting Ferrocene As A Way To Investigate Its Gas Phase Structure By Rotational Spectroscopy
Author(s)
Blanco, Susana
Contributor(s)
  • Alkorta, Ibon
  • Yáñez, Manuel
  • Lopez, Juan Carlos
  • Verde, Andres
Issue Date
2022-06-20
Keyword(s)
Structure determination
Abstract
In ferrocene (Fe(C$_{5}$H$_{5}$)$_{2}$), the first discovered metallocene, iron is sandwiched between two cyclopentadienyl rings in an eclipsed configuration. Ferrocene is an orange solid that sublimates easily and is stable at high temperatures. Due to its symmetry (D$_{5h}$) this compound does not have a dipole moment, so it is not active in the microwave region and consequently, its gas phase structure is not accessible through microwave spectroscopy. However, as it has been shown for triacetone triperoxide [1], its complexation with water makes it possible. In this work, we have done a combined theoretical and experimental work to observe and analyze the microwave spectrum of ferrocene – H$_{2}$O. The theoretical computations predict two possible low-energy structures of the complex. In one form, water lies in the $\sigma$$_{h}$ plane of ferrocene. In the other form, water is close to the C$_{5}$ axis of ferrocene on top of one of the cyclopentadienyl rings. Both forms have been observed. The most intense spectrum is that of a symmetric top with satellite patterns consistent with the effects of the free rotation of water. The rotational constant B determined for this spectrum is close to that predicted for the second axial form so that we can conclude that water is located along the C$_{5}$ axis and freely rotating around it. This motion averages the ferrocene – H$_{2}$O structure to that of a symmetric top. Different isotopic species have been detected, including $^{54}$Fe and $^{13}$C in their natural abundances, which have made it possible to determine the structure of the heavy atom skeleton of ferrocene and the axial location of water. A second weaker rotamer with an asymmetric top spectrum has rotational constants very close to those predicted for the other ferrocene-water conformer. Experimental and theoretical work is still in progress. 1. Blanco, S.; Macario, A.; Garcia-Calvo, J.; Revilla-Cuesta, A.; Torroba, T.; Lopez, J.C.; Microwave Detection of Wet Triacetone Triperoxide (TATP: Non-Covalent Forces and Water Dynamics. Chem. Eur. J. 2021, 27, 1680–1687.
Publisher
International Symposium on Molecular Spectroscopy
Type of Resource
text
Genre of Resource
Conference Paper / Presentation
Language
eng
Handle URL
https://hdl.handle.net/2142/116977
DOI
https://doi.org/10.15278/isms.2022.MI03
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Copyright 2022 held by the authors

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Abstracts & Presentations - 2022 International Symposium on Molecular Spectroscopy PRIMARY