Journal Article

PUBDB-2024-05470

http://join2-wiki.gsi.de/foswiki/pub/Main/Artwork/join2_logo100x88.png Unraveling the stereoisomer configurations of 1,1’-bis(tert-butylphosphino)ferrocene in the gas phase

Sun, W. (First author)DESY* ; Kargin, D. ; Kelemen, Z. ; Pietschnig, R. ; Schnell, M. (Corresponding author)CFEL*DESY*

2025
Wiley-VCH Verl. Weinheim

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Please use a persistent id in citations: doi:10.1002/cphc.202400881  doi:10.3204/PUBDB-2024-05470

Abstract: The molecular structure of a ferrocene derivative with adjacent centers of chirality, 1,1’-bis(tert-butylphosphino)ferrocene, has been examined in the gas phase using broadband microwave spectroscopy under the isolated and cold conditions of a supersonic jet. The diastereomers of 1,1’-bis(tert-butylphosphino)ferrocene can adopt homo- and hetero-chiral configurations, owing to the P-chiral substituents on the cyclopentadienyl rings. Moreover, the internal ring rotation of each diastereomer gives rise to four conformers with eclipsed ring arrangements, where the two tert-butylphosphino groups were separated by dihedral angles of approximately 72◦, 144◦,216◦, and 288◦ with respect to the two ring centers. The interconversion barriers between the conformations are below 2 kJ/mol, whereas the pyramidal inversion of the tert-butylphosphino groups is hindered by more than 140kJ/mol, calculated at the B3LYP-D3(BJ)/def2-QZVP level of theory. In the experimental microwave spectrum,we unambiguously identified the two global-minimum diastereomers with 72◦ conformations. The absence of otherconformers can be attributed to the relaxation dynamics in the supersonic jet, which transfers the high-energy conformers to the respective global-minimum geometries. Additionally, we discovered that London dispersion interactions between the two tert-butylphosphino groups play a crucial role in stabilizing the structures of this ferrocene complex.

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Contributing Institute(s):

1. Spectroscopy of molecular processes (FS-SMP)

Research Program(s):

1. 631 - Matter – Dynamics, Mechanisms and Control (POF4-631) (POF4-631)
2. SFB 1319 B02 - Enantiomerenunterscheidung, Trennung und Präzisionsuntersuchungen mittels zugeschnittener Mikrowellenfelder (B02) (389894861) (389894861)
3. DFG project G:(GEPRIS)328961117 - SFB 1319: Extremes Licht zur Analyse und Kontrolle molekularer Chiralität (ELCH) (328961117) (328961117)

Experiment(s):

1. No specific instrument

Appears in the scientific report 2024

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Database coverage:
; ; ; Clarivate Analytics Master Journal List ; Current Contents - Physical, Chemical and Earth Sciences ; DEAL Wiley ; Essential Science Indicators ; SCOPUS ; Science Citation Index Expanded ; Web of Science Core Collection

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