How an Internal Supramolecular Interaction Determines the Stereochemistry of a Metal Center

Author:

Steinmetz Maxime1,Gourlaouen Christophe2ORCID,Sémeril David1ORCID

Affiliation:

1. Synthèse Organométallique et Catalyse, UMR-CNRS 7177 Institut de Chimie de Strasbourg, Strasbourg University, 67008 Strasbourg, France

2. Laboratoire de Chimie Quantique, UMR-CNRS 7177 Institut de Chimie de Strasbourg, Strasbourg University, 67008 Strasbourg, France

Abstract

The chloro-P,N-{diphenylphosphanyl-[(5-phenyl-1,3,4-oxadiazol-2-ylamino)phenyl-me- thyl]}(p-cymene)ruthenium(II) hexafluorophosphate complex (4) was obtained in two steps from diphenylphosphanyl-[(5-phenyl-1,3,4-oxadiazol-2-ylamino)phenyl-methyl] borane (2). In the first step, the oxadiazole ring coordinated with the ruthenium atom, resulting in the formation of the dichloro-N-{diphenylphosphanyl-[(5-phenyl-1,3,4-oxadiazol-2-ylamino)phenyl-methyl]borane}(p-cymene) ruthenium(II) complex (3). During the crystallization of the P,N-chelate ruthenium complex, the formation of conglomerate crystals was revealed by X-ray structure analysis. Only two stereoisomers were obtained with (S)-Ru and (R)-C configurations in the first complex and with (R)-Ru and (S)-C configurations in the second. This deracemization during crystallization is due to the formation of a hydrogen bond between the P,N-ligand and the chlorine atom (CH•••Cl). This supramolecular interaction allows the transfer of the ligand chirality to the metal center and decrees the stereochemistry of the ruthenium atom.

Publisher

MDPI AG

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