Sebli, Cynthia Paul, Howson, Suzanne E., Clarkson, Guy J. and Scott, Peter, 1965 Dec. 10-. (2010) fac-Specific syntheses of homochiral [Fe(NN ')(3)](2+) complexes (NN ' = pyridine keto-hydrazone); origins of the stereoselectivity. Dalton Transactions, Vol.39 (No.18). pp. 4447-4454. ISSN 1477-9226

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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 pi-pi 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 t(1/2) 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 [FeL27(CH3CN)(2)](2+) are readily available.

Item Type:	Journal Article
Subjects:	Q Science > QD Chemistry
Divisions:	Faculty of Science > Chemistry
Library of Congress Subject Headings (LCSH):	Stereochemistry, Pyridine, Chelates, Complex compounds -- Synthesis
Journal or Publication Title:	Dalton Transactions
Publisher:	Royal Society of Chemistry
ISSN:	1477-9226
Date:	2010
Volume:	Vol.39
Number:	No.18
Number of Pages:	8
Page Range:	pp. 4447-4454
Identification Number:	10.1039/c000815j
Status:	Peer Reviewed
Publication Status:	Published
Funder:	Engineering and Physical Sciences Research Council (EPSRC), Yayasan Sarawak Tunku Abdul Rahman Sarawak Scholarship Scheme
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URI:	http://wrap.warwick.ac.uk/id/eprint/6040

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