Directed Dynamic Resolution of an Atropisomeric Silver Complex in Solution: Role of π–π Interactions

We report a directed dynamic resolution process for an atropisomeric [Ag(NHC)<sub>2</sub>]<sup>+</sup> complex, where stereochemical control is achieved through enantiomeric interconversion in solution before crystallization. Unlike conventional diastereomeric salt formation, our approach shifts the restricted interconversion between <i>R</i><sub>a</sub> and <i>S</i><sub>a</sub> atropisomers, allowing selective stabilization of one enantiomer via π-π interactions with enantiopure binaphthalene-based borate anions in solution. NMR spectroscopy reveals conformational locking and restricted dynamics preceding crystallization, which captures the resolved stereochemistry in highly crystalline salts. This study demonstrates that noncovalent interactions effectively modulate molecular conformational dynamics to achieve chiral resolution.

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Publication Details

Journal
Inorganic Chemistry
Published
2025-11-05
DOI
https://doi.org/10.1021/acs.inorgchem.5c03548
Primary Topic
N-Heterocyclic Carbenes in Organic and Inorganic Chemistry
Type
article
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article

Directed Dynamic Resolution of an Atropisomeric Silver Complex in Solution: Role of π–π Interactions

Alvaro Polo, Ricardo Rodrı́guez, Pablo J. Sanz Miguel
Inorganic Chemistry
N-Heterocyclic Carbenes in Organic and Inorganic Chemistry
article

Directed Dynamic Resolution of an Atropisomeric Silver Complex in Solution: Role of π–π Interactions

Alvaro Polo, Ricardo Rodrı́guez, Pablo J. Sanz Miguel
article en

Abstract

We report a directed dynamic resolution process for an atropisomeric [Ag(NHC)<sub>2</sub>]<sup>+</sup> complex, where stereochemical control is achieved through enantiomeric interconversion in solution before crystallization. Unlike conventional diastereomeric salt formation, our approach shifts the restricted interconversion between <i>R</i><sub>a</sub> and <i>S</i><sub>a</sub> atropisomers, allowing selective stabilization of one enantiomer via π-π interactions with enantiopure binaphthalene-based borate anions in solution. NMR spectroscopy reveals conformational locking and restricted dynamics preceding crystallization, which captures the resolved stereochemistry in highly crystalline salts. This study demonstrates that noncovalent interactions effectively modulate molecular conformational dynamics to achieve chiral resolution.

Inorganic ChemistryVol. 65(3)
Instituto de Síntesis Química y Catálisis Homogénea (ES)
Openalex Percentile: Top 75%
N-Heterocyclic Carbenes in Organic and Inorganic Chemistry
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