UNSPECIFIED (2003) Synthesis and X-ray crystal structures of iron(II) and manganese(II) complexes of unsubstituted and benzyl substituted cross-bridged tetraazamacrocycles. Inorganica Chimica Acta, 346 . pp. 76-86. ISSN 0020-1693

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Abstract

The Mn2+ and Fe2+ complexes of the cross-bridged tetraazamacrocyclic ligands, 4,11-dibenzyl-1,4,8,11-tetraazabicyclo[6.6.2]hexadecane (1), 4,10-dibenzyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecane (2), 1,4,8,11-tetraazabicyclo[6.6.2]hexadecane (3), and 1,4,7,10-tetraazabicyclo[5.5.2]tetradecane (4) provide new compounds of these elements for fundamental studies and applications. These unsubstituted and benzyl substituted derivatives were prepared for comparison of their structures and properties with the known catalytically active dimethyl cross-bridged ligand complexes, which are especially notable for their exceptional kinetic stabilities and redox activity. The X-ray crystal structures of five complexes demonstrate that the ligands enforce a distorted octahedral geometry on the metals with two cis sites occupied by labile ligands. The Fe2+ complexes of the unsubstitued ligands form mu-oxo dimers upon exposure to air, which have also been structurally characterized. Cyclic voltammetry of the monomeric complexes shows reversible redox processes for the M3+/M2+ couples, which are sensitive to solvent, ring size, and ring substitution. (C) 2002 Elsevier Science B.V. All rights reserved.

Item Type:	Journal Article
Subjects:	Q Science > QD Chemistry
Journal or Publication Title:	Inorganica Chimica Acta
Publisher:	ELSEVIER SCIENCE SA
ISSN:	0020-1693
Date:	25 March 2003
Volume:	346
Number of Pages:	11
Page Range:	pp. 76-86
Publication Status:	Published
URI:	http://wrap.warwick.ac.uk/id/eprint/9900

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