Issue 18, 2016

C3-symmetry Mo3S4 aminophosphino clusters combining three sources of stereogenicity: stereocontrol directed by hydrogen bond interactions and ligand configuration

Abstract

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.

Graphical abstract: C3-symmetry Mo3S4 aminophosphino clusters combining three sources of stereogenicity: stereocontrol directed by hydrogen bond interactions and ligand configuration

Supplementary files

Article information

Article type
Paper
Submitted
25 Feb 2016
Accepted
24 Mar 2016
First published
11 Apr 2016
This article is Open Access
Creative Commons BY-NC license

Dalton Trans., 2016,45, 7829-7835

C3-symmetry Mo3S4 aminophosphino clusters combining three sources of stereogenicity: stereocontrol directed by hydrogen bond interactions and ligand configuration

C. Alfonso, M. Feliz, V. S. Safont and R. Llusar, Dalton Trans., 2016, 45, 7829 DOI: 10.1039/C6DT00755D

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