Becker, Jan M., Barker, J. (James), Clarkson, Guy J., van Gorkum, Remy, Johal, Gursharon K., Walton, Richard I. and Scott, Peter, 1965 Dec. 10-. (2010) Chirality and diastereoselection in the mu-oxo diiron complexes L2Fe-O-FeL2 (L = bidentate salicylaldiminato). Dalton Transactions, Vol.39 (No.9). pp. 2309-2326. ISSN 1477-9226

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Abstract

A number of bis(salicylaldiminato) (Schiff base) complexes of Fe(II) i.e. L2Fe with a variety of ligand substituents and functionality are synthesised, usually by salt metathesis but on one occasion via the (sal)(2)Fe complex, and characterised by standard methods. Two molecular structure determinations indicate the expected tetrahedral geometry. Treatment with dry oxygen yielded the Fe(III) complexes [(FeL2)(2)-mu-O], generally in high yield and in the absence of hydroxylated impurities; one bulky complex L2Fe gave no oxidation product for steric reasons, and one hydroxyl-substituted compound gave an insoluble product. Five molecular structures of these [(FeL2)(2)-mu-O] compounds were determined. All were homochiral in the sense that the absolute configuration at Fe was the same for both atoms. Three of the structures-those based on optically pure salicylaldimine ligands-were diastereomeric. For two, the diastereomers observed are those predicted on the basis of steric considerations, while a third highly distorted and congested structure represents the unexpected diastereomer. Powder X-ray diffraction confirms high phase purity of the bulk samples (i.e. they are diastereomerically pure to the level detectable). These investigations, coupled with molecular structure and NMR studies on model gallium complexes, indicate that the diastereoselection arises from cooperative interactions across the oxo bridge.

Item Type:	Journal Article
Subjects:	Q Science > QD Chemistry
Divisions:	Faculty of Science > Chemistry
Library of Congress Subject Headings (LCSH):	Chirality, Diastereoisomers, Iron
Journal or Publication Title:	Dalton Transactions
Publisher:	Royal Society of Chemistry
ISSN:	1477-9226
Date:	2010
Volume:	Vol.39
Number:	No.9
Number of Pages:	18
Page Range:	pp. 2309-2326
Identification Number:	10.1039/b905706d
Status:	Peer Reviewed
Publication Status:	Published
Funder:	Engineering and Physical Sciences Research Council (EPSRC)
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URI:	http://wrap.warwick.ac.uk/id/eprint/6007

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