Zabka, Matej and Naviri, Lavakumar and Gschwind, Ruth M. (2021) Noncovalent CH-pi and pi-pi Interactions in Phosphoramidite Palladium(II) Complexes with Strong Conformational Preference. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 60 (49). pp. 25832-25838. ISSN 1433-7851, 1521-3773
Full text not available from this repository. (Request a copy)Abstract
The weak noncovalent interactions and flexibility of ligands play a key role in enantioselective metal-catalyzed reactions. In transition metal complexes and their catalytic applications, the experimental assessment and the design of key interactions is as difficult as the prediction of the enantioselectivities, especially for flexible, privileged ligands such as chiral phosphoramidites. Therefore, the interligand interactions in cis-(PdL2Cl2)-L-II phosphoramidite complexes were investigated by NMR spectroscopy and computations. We were able to induce a strong conformational preference by breaking the symmetry of the C-2-symmetric side chain of one of the ligands, and shift the equilibrium between hetero- and homocomplexes towards heterocomplexes because of interligand interactions in the cis-complexes. The modulation of aryl substituents was exploited, along with the solvent effect. The combined CH-pi and pi-pi interactions reveal design patterns for binding and folding of chiral ligands and catalysts.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | ENANTIOSELECTIVE CONJUGATE ADDITION; FACE AROMATIC INTERACTIONS; MONODENTATE PHOSPHORAMIDITE; MOLECULAR RECOGNITION; LONDON DISPERSION; LIGANDS; BALANCE; HYDROGENATION; FORCES; CHEMISTRY; conformational analysis; NMR spectroscopy; noncovalent interactions; phosphoramidites; supramolecular balance |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Organische Chemie > Arbeitskreis Prof. Dr. Ruth Gschwind |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 05 Jul 2022 10:54 |
| Last Modified: | 05 Jul 2022 10:54 |
| URI: | https://pred.uni-regensburg.de/id/eprint/46089 |
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