Copper(II) chemistry of the functionalized macrocycle cyclam tetrapropionic acid
The CuII complex of H4TETP (H4TETP = 1,4,8,11-tetraazatetradecane-1,4,8,11-tetrapropionic acid) is five-coordinate with a distorted square-pyramidal structure (τ = 0.45; i.e. the geometry is nearly half-way between square-pyramidal and trigonal-bipyramidal) and a relatively long Cu-N and a short Cu-...
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| Main Authors: | , , |
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| Format: | Article (Journal) |
| Language: | English |
| Published: |
2013
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| In: |
Dalton transactions
Year: 2012, Volume: 42, Issue: 17, Pages: 6142-6148 |
| ISSN: | 1477-9234 |
| DOI: | 10.1039/C2DT32356G |
| Online Access: | Verlag, Volltext: http://dx.doi.org/10.1039/C2DT32356G Verlag, Volltext: https://pubs.rsc.org/en/content/articlelanding/2013/dt/c2dt32356g 
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| Author Notes: | Peter Comba, Franziska Emmerling, Maik Jakob, Werner Kraus, Manja Kubeil, Michael Morgen, Jens Pietzsch and Holger Stephan |
| Summary: | The CuII complex of H4TETP (H4TETP = 1,4,8,11-tetraazatetradecane-1,4,8,11-tetrapropionic acid) is five-coordinate with a distorted square-pyramidal structure (τ = 0.45; i.e. the geometry is nearly half-way between square-pyramidal and trigonal-bipyramidal) and a relatively long Cu-N and a short Cu-O bond; the comparison between powder and solution electronic spectroscopy, the frozen solution EPR spectrum and ligand-field-based calculations (angular overlap model, AOM) indicate that the solution and solid state structures are very similar, i.e. the complex has a relatively low “in-plane” and a significant axial ligand field with a dx2−y2 ground state. The ligand-enforced structure is therefore shown to lead to a partially quenched Jahn-Teller distortion and to a relatively low complex stability, lower than with the corresponding acetate-derived ligand H4TETA. This is confirmed by potentiometric titration and by the biodistribution with 64Cu-labeled ligands which show that the uptake in the liver is significantly increased with the H4TETP-based system. |
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| Item Description: | First published 27 Nov 2012 Gesehen am 17.08.2018 |
| Physical Description: | Online Resource |
| ISSN: | 1477-9234 |
| DOI: | 10.1039/C2DT32356G |