Blue copper protein analogue: synthesis and characterization of copper complexes of the N2S2 macrocycle 1, 8-dithia-4, 11-diazacyclotetradecane. Issue 46 (4th November 2015)

• Record Type: Journal Article
• Authors: Walker, Tia L.; Mula, Sam; Malasi, Wilhelm; Engle, James T.; Ziegler, Christopher J.; van der Est, Art; Modarelli, Jody; Taschner, Michael J.
• Is Part Of: Dalton transactions. Volume 44:Issue 46(2015)
• Page Start: 20200
• Page End: 20206
• Publication Date: 2015-11-04
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/c5dt03389f
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : We report the synthesis, spectroscopic characterization and X-ray crystal structures of Cu I/II complexes prepared from the N2 S2 macrocycle 1, 8-dithia-4, 11-diazacyclotetradecane. Abstract : 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 inFig. 1, 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 complex2 . 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 complex2 in CH3 CN is +403 mV versus NHE.