Type 1 copper site synthetic model complexes with increased redox potentials |
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Authors: | Lei Yang William B. Tolman |
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Affiliation: | (1) Department of Chemistry and Center for Metals in Biocatalysis, University of Minnesota, 207 Pleasant St. SE, Minneapolis, MN 55455, USA;; |
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Abstract: | Reactions of NaSCPh3 with (R3tacn)Cu(OTf)2 (R is Me, iPr; tacn is 1,4,7-triazacyclononane; OTf is CF3SO3 −) yield blue complexes identified as ((R3tacn)CuSCPh3)(OTf) on the basis of UV–vis, resonance Raman, and electron paramagnetic resonance (EPR) spectroscopy and electrospray ionization mass spectrometry. These complexes exhibit spectroscopic properties typical of type 1 copper sites in proteins, including diagnostic Sπ → Cu(dx2 - y2 ) (d_{{x^{2} - y^{2} }} ) ligand-to-metal charge transfer transitions at approximately 610–630 nm and small A || values in EPR spectra of less than 100 × 10−4 cm−1. Cyclic voltammetry experiments revealed redox potentials for the complexes similar to those of several low-potential type 1 copper proteins (e.g., azurin, stellacyanin) and approximately 0.5 V higher than those of previously reported model compounds. Thus, the new complexes mimic key aspects of both the structure and the function of type 1 copper sites. |
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