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Copper(II), iron(III) and cobalt(III) complexes of the pendent-arm cyclam derivative 6,6,13-trimethyl-13-amino-1,4,8,11-tetraazacyclotetradecane

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Abstract

The interaction of Cu(II), Fe(III) and Co(III) with 6,6,13-trimethyl-13-amino-1,4,8,11-tetraazacyclotetradecane (L 3) incorporating a pendent amine group has led to isolation of the new octahedral complexes [Cu(HL 3)(ClO4)2]Cl·H2O (1), [Fe(L 3)Cl](S2O6)·H2O (2), [Co(L 3)Cl](ClO4)1.5Cl0.5·0.25H2O (3), [Co(HL 3)Cl2](ClO4)2·H2O (4) and [Co(L 3)Cl]2(S2O4)(ClO4)2 (5). In (1) the copper ion occupies the macrocyclic cavity of protonated (–NH3 +) L 3 which is present in its trans-III configuration; weakly bound ClO4 − ligands occupy the axial positions. The X-ray structure of (2) showed that Fe(III) occupies the N4-macrocyclic cavity of L 3 in a trans-III configuration, with the pendent amine group binding in an axial position. The remaining axial position is occupied by a Cl− ligand. Chromatography of the product obtained from the reaction of Na3[Co(CO3)3] with L 3 yielded three fractions. Fraction 1 yielded crystals (3) composed of three crystallographically independent species incorporating cations of type [Co(L 3)Cl]2+ with very similar structures; in each case the macrocyclic ring nitrogens of L 3 are bound to the Co(III) in an asymmetric cis-fashion. Fraction 2 yielded the trans-III octahedral cationic complex (4) incorporating L 3 in its protonated form. The Co(III) complex (5) from fraction 3 shows a different coordination arrangement to the products from fractions 1 or 2. The macrocyclic ring coordinates in its trans-III form, but the axial sites in this case are occupied by the pendent-NH2 group and a Cl− ligand.

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Notes

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Acknowledgements

Authors gratefully acknowledge Kosin University and the Australian Research Council for support.

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Authors and Affiliations

  1. School of Chemistry, The University of Sydney, Sydney, NSW, 2006, Australia

    Jack K. Clegg & Leonard F. Lindoy

  2. CEA, IRAMIS, SIS2 M, LCCEf (CNRS URA 331), Bâtiment 125, 91191, Gif-sur-Yvette, France

    Pierre Thuéry

  3. Department of Chemistry and Advanced Materials, Kosin University, 149-1, Dongsam-dong, Yeongdo-gu, Busan, 606-701, South Korea

    Young Hoon Lee, Dewi K. A. Kusumohastuti, Cindy Mora, Hyang Hoo Kim, Jeong Hwan Cho & Yang Kim

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Correspondence to Yang Kim.

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Authors dedicate this manuscript to Prof. Jack Harrowfield and Dr. Jacques Vicens in celebration of their 65th birthdays.

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Supplementary data (selected bond distances and angles for the X-ray structures) associated with this article is given below.

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Clegg, J.K., Lindoy, L.F., Thuéry, P. et al. Copper(II), iron(III) and cobalt(III) complexes of the pendent-arm cyclam derivative 6,6,13-trimethyl-13-amino-1,4,8,11-tetraazacyclotetradecane. J Incl Phenom Macrocycl Chem 65, 49–57 (2009). https://doi.org/10.1007/s10847-009-9625-7

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