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Dependence of the Properties of Cobalt(iii) Cage Complex as a Function of the Derivatization of Amine Substituents
Alan M.
Sargeson A B,
Peter A.
Lay A C D
A
Research School of Chemistry, Building 35, Australian National University, Canberra, ACT 0200, Australia.
B
Deceased. This manuscript is dedicated to Alan Sargeson who was an important influence on the development of my academic career through his mentoring, collaboration, and friendship.
C
School of Chemistry, The University of Sydney, NSW 2006, Australia.
D
Corresponding author. Email: p.lay@chem.usyd.edu.au
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Australian Journal of Chemistry 62(10) 1280–1290 http://dx.doi.org/10.1071/CH09368
Submitted: 29 June 2009
Accepted: 20 August 2009
Published online: 13 October 2009
Abstract
Control of redox properties of cobalt macrobicyclic hexaamine (cage) complexes by substituent modification is important for their use as electron-transfer agents, and the resultant derivatives can also change the lipophilicity of the complexes for a variety of biological and other applications. Such derivatization is also important for incorporating cage complexes into a range of redoxactive conjugates. Here, the derivatization of the amine groups in the 1 and 8 positions of [Co(sar)]3+ (sar = sarcophagine = 3,6,10,13,16,19-hexaazabicyclo[6.6.6]icosane) are reported. The synthesis and properties of methylamide (from the reactions with acetic anhydride), arylimine (from Schiff base reactions), benzylamine, phthalimido, and tosylate derivatives are described. These reactions provide synthons that have the potential to act as precursors for building a range of conjugates containing metal cage complexes, including dimers. The effects of the substituents on the ligand conformations, which affect other chemical and physical properties of the cage complexes, are discussed.
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