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- W2034736032 abstract "Two-dimensional exchange NMR spectroscopy has been employed to study the isomerization process of copper(I) complexes formed upon complexation of Cu+ with a racemic mixture of the atropoisomer diimine benzimidazole−pyridine ligands 1−3 and evaluate the configurational stability of the pseudotetrahedral complexes [Cu(1−3)2]PF6. Racemization of the heterochiral isomers RSΛ/RSΔ proceeds through an intramolecular ligand rearrangement on a time scale of about 1.9 s-1 for 1, 4.4 s-1 for 2, and 0.3 s-1 for 3 in CD2Cl2 at room temperature. The intramolecular Λ/Δ isomerizations in the homochiral diastereoisomers RRΔ/SSΛ and RRΛ/SSΔ of [Cu(1)2]PF6 proceed at room temperature on a time scale of about 0.6 s-1 for the conversion of RRΔ/SSΛ into RRΛ/SSΔ and 13 s-1 for the conversion of RRΛ/SSΔ into RRΔ/SSΛ. The kinetics of these intramolecular exchange processes were found to be sensitive to the stabilizing interligand π-stacking interactions that develop within the [Cu(1−3)2]+ structure and to the bulkiness of the benzimidazole aryl substituents. The kinetics of racemization in the heterochiral RSΛ/RSΔ isomers of [Cu(3)2]PF6 with the bulky cumyl-derived ligand were 1 order of magnitude lower than in [Cu(2)2]PF6 with the tolyl-based ligand. Slower intermolecular ligand exchanges between all the isomers have also been shown to occur at ambient temperature in CD2Cl2 through complete ligand dissociation. Free energies at 298 K varying between 66.7 and 74.4 kJ·mol-1 and entropies varying between −26.4 and 28.3 J·K-1·mol-1 were determined for the intramolecular Λ/Δ isomerizations. For the intermolecular ligand exchanges free energies at 298 K varying between 55.6 and 62.5 kJ·mol-1 and entropies varying between −97.9 and −74.5 J·K-1·mol-1 were measured." @default.
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- W2034736032 date "2004-04-02" @default.
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- W2034736032 title "Isomerization Dynamics in Homo- and Heterochiral Atropoisomer Copper(I) Diimine Complexes: A 2D EXSY NMR Study" @default.
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- W2034736032 doi "https://doi.org/10.1021/ic0353108" @default.
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