TY  - JOUR
AU  - Sun, Wenhao
AU  - Kargin, Denis
AU  - Kelemen, Zsolt
AU  - Pietschnig, Rudolf
AU  - Schnell, Melanie
TI  - Unraveling the stereoisomer configurations of 1,1’-bis(tert-butylphosphino)ferrocene in the gas phase
JO  - ChemPhysChem
VL  - 26
IS  - 5
SN  - 1439-4235
CY  - Weinheim
PB  - Wiley-VCH Verl.
M1  - PUBDB-2024-05470
SP  - e202400881
PY  - 2025
AB  - 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.
LB  - PUB:(DE-HGF)16
C6  - pmid:39565666
UR  - <Go to ISI:>//WOS:001377577100001
DO  - DOI:10.1002/cphc.202400881
UR  - https://bib-pubdb1.desy.de/record/612805
ER  -