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Copper( ii ) chemistry of the functionalized macrocycle cyclam tetrapropionic acid

Comba, Peter ; Emmerling, Franziska ; Jakob, Maik ; Kraus, Werner ; Kubeil, Manja ; Morgen, Michael ; Pietzsch, Jens ; Stephan, Holger

Dalton Transactions, Dalton Transactions, 2013, Vol.42(17), pp.6142-6148 [Periódico revisado por pares]

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  • Título:
    Copper( ii ) chemistry of the functionalized macrocycle cyclam tetrapropionic acid
  • Autor: Comba, Peter ; Emmerling, Franziska ; Jakob, Maik ; Kraus, Werner ; Kubeil, Manja ; Morgen, Michael ; Pietzsch, Jens ; Stephan, Holger
  • Assuntos: Chemistry
  • É parte de: Dalton Transactions, Dalton Transactions, 2013, Vol.42(17), pp.6142-6148
  • Descrição: The Cu II complex of H 4 TETP (H 4 TETP = 1,4,8,11-tetraazatetradecane-1,4,8,11-tetrapropionic acid) is five-coordinate with a distorted square-pyramidal structure ( = 0.45; i.e. the geometry is nearly half-way between square-pyramidal and trigonal-bipyramidal) and a relatively long CuN and a short CuO 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 d x 2 y 2 ground state. The ligand-enforced structure is therefore shown to lead to a partially quenched JahnTeller distortion and to a relatively low complex stability, lower than with the corresponding acetate-derived ligand H 4 TETA. This is confirmed by potentiometric titration and by the biodistribution with 64 Cu-labeled ligands which show that the uptake in the liver is significantly increased with the H 4 TETP-based system.

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