Chiral recognition and resolution of the enantiomers of supramolecular triangular hosts: synthesis, circular dichroism, NMR, and X-ray molecular structure of [Li subset(R,R,R)-[CpRh(5-chloro-2,3-dioxopyridine)]3][Delta-Trisphat]

Lamia Mimassi; Carine Guyard-Duhayon; Marie Noelle Rager; Hani Amouri

doi:10.1021/ic049361w

Chiral recognition and resolution of the enantiomers of supramolecular triangular hosts: synthesis, circular dichroism, NMR, and X-ray molecular structure of [Li subset(R,R,R)-[CpRh(5-chloro-2,3-dioxopyridine)]3][Delta-Trisphat]

Inorg Chem. 2004 Oct 18;43(21):6644-9. doi: 10.1021/ic049361w.

Authors

Lamia Mimassi¹, Carine Guyard-Duhayon, Marie Noelle Rager, Hani Amouri

Affiliation

¹ Laboratoire de Chimie Inorganique et Matériaux Moléculaires, UMR CNRS 7071, Université Pierre et Marie Curie Paris VI, 4 place Jussieu, case 42, 75252 Paris Cedex 05, France.

PMID: 15476363
DOI: 10.1021/ic049361w

Abstract

The racemic triangular supramolecular host [CpRh(5-chloro-2,3-dioxopyridine)](3) (1) was prepared in high yield. Treatment with LiCl followed by addition of silver salt AgOTf gave the triflate salt species [Li subset[CpRh(5-chloro-2,3-dioxopyridine)](3)][OTf] (2). Subsequent anion metathesis using the optically pure chiral shift reagent [Cinchonidinium][Delta-Trisphat] produced a pair of diastereomers [Li subset(R,R,R)-[CpRh(5-chloro-2,3-dioxopyridine)](3)][Delta-Trisphat] (3a) and [Li subset(S,S,S)-[CpRh(5-chloro-2,3-dioxopyridine)](3)][Delta-Trisphat] (3b). The resolution of these diastereomers was achieved by fractional crystallization, and their stereochemistry relationship was established by circular dichroism studies. The X-ray molecular structure of 3a is reported and shows as an outstanding feature a chiral recognition between the Delta-Trisphat anion and a single enantiomer cation [Li subset(R,R,R)-[CpRh(5-chloro-2,3-dioxopyridine)](3)](+) manifested through a pi-pi interaction. (1)H NMR and circular dichroism studies in solution support the solid-state behavior.