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• W2094711030 endingPage "4447" @default.
• W2094711030 startingPage "4447" @default.
• W2094711030 abstract "The 2-pyridinehydrazones (from condensation of pyridine-2-carbaldehyde and hydrazines) have previously been noted to have poor ligating ability as a result of a sterically demanding planar conformation. Destabilisation of this conformation is achieved through simple use of the ketohydrazones, and as a result the diamagnetic chiral tris-bidentate diimine complexes fac-[FeL3]2+ are readily isolated. In the solid state, inter-ligand π–π stacking and complex/counter-ion H-bonding are apparent, and these features persist in solution according to dynamic NMR spectra, which also indicate extremely high stereoselectivity for the fac isomers (>200 : 1). The compounds crystallise as conglomerates, and time-resolved CD spectra of non-racemic samples indicate a high degree of persistence of chirality (racemisation t1/2ca 77 min). Variations of solvent and counter-ion indicate that H-bonding is unimportant in determining the structure of the cation. The fac-selectivity arises in the induction of a chiral conformation in the coordinated ligand, and the fact that such non-planar ligands can only be accommodated about the Fe(II) centre if they all have the same absolute configuration. Adding a hydrazine N-methyl group increases the steric demand further, while retaining the novel non-planar conformation, and as a result paramagnetic chiral bis-bidentate complexes such as [FeL72(CH3CN)2]2+ are readily available." @default.
• W2094711030 created "2016-06-24" @default.
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• W2094711030 creator A5051966189 @default.
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• W2094711030 date "2010-01-01" @default.
• W2094711030 modified "2023-09-25" @default.
• W2094711030 title "fac-Specific syntheses of homochiral [Fe(NN′)3]2+ complexes (NN′ = pyridine keto-hydrazone); origins of the stereoselectivity" @default.
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• W2094711030 doi "https://doi.org/10.1039/c000815j" @default.
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