title: fac-Specific syntheses of homochiral [Fe(NN)3]2+ complexes (NN = pyridine keto-hydrazone); origins of the stereoselectivity.
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 - 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 t1/2 ca 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.
authors.affiliation: Department of Chemistry, University of Warwick, Gibbet Hill Road, Coventry, UK CV4 7AL.
authors.forename: Cynthia Paul
authors.initials: CP
authors.lastname: Sebli
authors.forename: Suzanne E
authors.initials: SE
authors.lastname: Howson
authors.forename: Guy J
authors.initials: GJ
authors.lastname: Clarkson
authors.forename: Peter
authors.initials: P
authors.lastname: Scott