Slow Inversion of Coordinated Thioether Groups in SNS‐Type Ruthenium Pincer Complexes

The thioether‐group‐containing SNS‐type pincer complex [({EtSCH 2 CH 2 } 2 NH)RuCl(H)(PPh 3 )] ( 2 ) exists in three different diastereomers ( 2 a – c ). The molecular structures obtained from single crystal X‐Ray diffraction studies of all three isomers reveal a difference in the relative orientati...

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Bibliographic Details
Published in:European journal of inorganic chemistry 2023-10, Vol.26 (28)
Main Authors: Rummel, Frederik, Wehmeyer, Frerk, Vogt, Matthias, Langer, Robert
Format: Article
Language:English
Subjects:
Inorganic chemistry
Isomers
Line shape
Molecular structure
NMR spectroscopy
Ruthenium
Single crystals
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Summary:The thioether‐group‐containing SNS‐type pincer complex [({EtSCH 2 CH 2 } 2 NH)RuCl(H)(PPh 3 )] ( 2 ) exists in three different diastereomers ( 2 a – c ). The molecular structures obtained from single crystal X‐Ray diffraction studies of all three isomers reveal a difference in the relative orientation of the respective EtS‐groups, while other commonly observed diastereomers as the result of cis ‐/ trans ‐ or fac ‐/ mer ‐isomerism are not observed. Chemical exchange between the three diastereomers 2 a – c was discovered by phase‐sensitive 1 H and 31 P NOESY NMR spectroscopy, and further quantified by line shape analysis of 1 H NMR spectra. The experimentally derived averaged Gibbs energies of activation for the interconversion of the isomers (65–70 kJ/mol) are in good agreement with the results obtained from DFT calculations, which suggest an inversion of the ligating sulfur atoms, although a dissociative pathway for the configurational inversion can be competitive.
ISSN:1434-1948
1099-0682
DOI:10.1002/ejic.202300313