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Manganese (III) cyclam complexes with aqua, iodo, nitrito, perchlorato and acetic acid/acetato axial ligands |
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| Authors: | Susanne Mossin Henning Osholm Sørensen Høgni Weihe Inger Søtofte |
| Institution: | a Department of Chemistry, University of Copenhagen, Universitetsparken 5, DK-2100 Copenhagen Ø, Denmark b Centre for Crystallographic Studies, Department of Chemistry, University of Copenhagen, Universitetsparken 5, DK-2100 Copenhagen Ø, Denmark c Department of Chemistry, Building 207, Technical University of Denmark, DK-2800 Kgs. Lyngby, Denmark |
| Abstract: | The syntheses, structures and magnetic properties of five new manganese (III) cyclam complexes, trans-Mn(cyclam)(OH2)2](CF3SO3)3 · H2O, trans-Mn(cyclam)I2]I, trans-Mn(cyclam)(ONO)2]ClO4, trans-Mn(cyclam)(OClO3)2]ClO4 and trans-Mn(cyclam)(CH3COO)(CH3COOH)](ClO4)2, are reported. Cyclam is the tetradentate amine ligand 1,4,8,11-tetraazacyclotetradecane. The complexes all exhibit pronounced tetragonal elongation of the coordination octahedron with the four cyclam nitrogens occupying the four equatorial positions. The magnetic properties are consistent with the formulation of the complexes as high-spin d4 systems. trans-Mn(cyclam)(OH2)2](CF3SO3)3 · H2O is shown to be a convenient starting material for the syntheses of trans cyclam complexes. Mn(cyclam)(CH3COO)(CH3COOH)](ClO4)2 exhibits extremely short intermolecular hydrogen bonds resulting in a pseudo-chain structure. The tilt of the axial ligands with respect to the equatorial plane containing the manganese and the cyclam nitrogen atoms is discussed. |
| Keywords: | Manganese (III) Synthesis X-ray Magnetism Axial tilt |
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