Blue copper protein analogue: synthesis and characterization of copper complexes of the N 2 S 2 macrocycle 1,8-dithia-4,11-diazacyclotetradecane

To improve understanding of copper at the active site of Type 1 copper proteins, Cu(I) and Cu(II) complexes of 1,8-dithia-4,11-diazacyclotetradecane, shown in , have been successfully isolated and structurally characterized by X-ray crystallography. In these compounds, both Cu(I) and Cu(II) are centered in the plane of the macrocycle containing two sulphur and two nitrogen heteroatoms comprising the distorted tetrahedral/square planar coordination geometry. The UV/VIS spectra, electrochemistry and EPR properties have been obtained for the Cu(II) complex 2. Three absorption bands at 295 nm, 354 nm, and 545 nm are observed in aqueous solution at a pH of 5. These bands have been assigned to the N → Cu(II) and S → Cu(II) charge transfer bands and the d-d transitions respectively. The Cu(I/II) redox midpoint potential of complex 2 in CH3CN is +403 mV versus NHE.