C3-symmetry Mo3S4 aminophosphino clusters combining three sources of stereogenicity: stereocontrol directed by hydrogen bond interactions and ligand configuration
| Autor: | Carmina Alfonso, Vicent S. Safont, Marta Feliz, Rosa Llusar |
|---|---|
| Jazyk: | angličtina |
| Rok vydání: | 2016 |
| Předmět: |
Circular dichroism
hydrogen bond interactions Bicyclic molecule 010405 organic chemistry Chemistry Hydrogen bond Ligand Stereochemistry Diastereomer 010402 general chemistry 01 natural sciences aminophosphino cubane-type Mo3S4 clusters Pyrrolidine 0104 chemical sciences Stereocenter ligand configuration Inorganic Chemistry chemistry.chemical_compound Cluster (physics) stereogenicity |
| Zdroj: | Repositori Universitat Jaume I Universitat Jaume I |
| Popis: | A diastereoselective synthesis of proline containing aminophosphino cubane-type Mo3S4 clusters, (P)-[Mo3S4Cl3((1S,2R)-PPro)3]Cl ((P)-[Mo-(SN,RC)]Cl) and (P)-[Mo3S4Cl3((1S,2S)-PPro)3]Cl ((P)-[Mo-(SN,SC)] Cl), has been achieved in high yields by reacting the corresponding enantiomerically pure PPro ((R)- and (S)-2-[(diphenylphosphino)methyl]pyrrolidine) ligands with the Mo3S4Cl4(PPh3)3(H2O)2 complex. Circular dichroism, nuclear magnetic resonance and X-ray techniques confirm that the (P)-[Mo-(SN,RC)]Cl and (P)-[Mo-(SN,SC)]Cl cluster cations are diastereoisomers which combine three sources of stereogenicity provided by the cluster framework, one carbon atom of the aminophosphine ligand and the nitrogen stereogenic center. The higher stability of the (P)-[Mo-(SN,SC)]+ cation is due to stabilizing vicinal Cl⋯HN interactions as well as due to the cis-fused conformation of the bicyclic system formed upon coordination of the aminophosphine ligand. The financial support of the Spanish Ministerio de Economía y Competitividad (Grant CTQ2011-23157 and CTQ2015-65207-P), Universitat Jaume I (Research Project P1·1B2013-19) and Generalitat Valenciana (PROMETEOII/2014/022) is gratefully acknowledged. The authors also thank the Servei Central d’Instrumentació Científica (SCIC) of the University Jaume I for providing us with the mass spectrometry, NMR and X-ray facilities. C. A. thanks the Spanish Ministerio de Economía y Competitividad for a predoctoral fellowship (FPI). |
| Databáze: | OpenAIRE |
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