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Three coordinate models for the binuclear CuA electron-transfer site
| Content Provider | Semantic Scholar |
|---|---|
| Author | Zhang, Shijun Warren, Timothy H. |
| Copyright Year | 2013 |
| Abstract | Truly three coordinate CuA synthetic models were developed by employing bulky N-heterocyclic carbene ligands along with simple C3 and C4 dithiolate linkers to emulate the role of histidine and cysteine ligands at trigonal copper sites. The reduced [CuICuI] models [NHC]Cu–S(CH2)nS–Cu[NHC] (n = 3 (3), 4 (4)) were characterized by NMR and X-ray crystallography. The structure of the reduced model with the C3 linker closely mimics the low coordinate, trigonal environment at the reduced dinuclear CuA site while the C4 linker resulted in an “open” solid state structure with two coordinate Cu centers. Oxidized species 3++++ and 4+++ were observed by UV-vis and EPR spectroscopy upon the addition of [Cp2Fe]+ to 3 and 4, generating spectroscopic features similar to those of the dinuclear [Cu1.5Cu1.5]+ CuA resting state. Key spectroscopic features of 3++++ and 4+++ are low energy intervalence charge transfer bands centered near 1150 nm and EPR spectra indicating delocalization of the unpaired e− among two Cu centers. Electrochemistry of the oxidized [Cu2S2]+ models reveals reduction potentials (E1/2 = 0.11 V (3++++); 0.36 V (4+++) vs. NHE) similar to the CuA site in CcO (E1/2 = 0.22–0.30 V vs. NHE). |
| Starting Page | 1786 |
| Ending Page | 1792 |
| Page Count | 7 |
| File Format | PDF HTM / HTML |
| DOI | 10.1039/C3SC21936D |
| Volume Number | 4 |
| Alternate Webpage(s) | http://www.rsc.org/suppdata/sc/c3/c3sc21936d/c3sc21936d.pdf |
| Alternate Webpage(s) | https://doi.org/10.1039/C3SC21936D |
| Language | English |
| Access Restriction | Open |
| Content Type | Text |
| Resource Type | Article |
