Issue 46, 2015

Blue copper protein analogue: synthesis and characterization of copper complexes of the N2S2 macrocycle 1,8-dithia-4,11-diazacyclotetradecane

Abstract

To improve understanding of copper at the active site of Type 1 copper proteins, CuI and CuII complexes of 1,8-dithia-4,11-diazacyclotetradecane, shown in Fig. 1, have been successfully isolated and structurally characterized by X-ray crystallography. In these compounds, both CuI and CuII 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 CuII 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 → CuII and S → CuII charge transfer bands and the d–d transitions respectively. The CuI/II redox midpoint potential of complex 2 in CH3CN is +403 mV versus NHE.

Graphical abstract: Blue copper protein analogue: synthesis and characterization of copper complexes of the N2S2 macrocycle 1,8-dithia-4,11-diazacyclotetradecane

Supplementary files

Article information

Article type
Paper
Submitted
31 Aug 2015
Accepted
23 Oct 2015
First published
04 Nov 2015

Dalton Trans., 2015,44, 20200-20206

Blue copper protein analogue: synthesis and characterization of copper complexes of the N2S2 macrocycle 1,8-dithia-4,11-diazacyclotetradecane

T. L. Walker, S. Mula, W. Malasi, J. T. Engle, C. J. Ziegler, A. van der Est, J. Modarelli and M. J. Taschner, Dalton Trans., 2015, 44, 20200 DOI: 10.1039/C5DT03389F

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