Document Type
Article
Language
eng
Publication Date
8-8-2015
Publisher
American Chemical Society
Source Publication
Inorganic Chemistry
Source ISSN
1520-510x
Original Item ID
DOI: 10.1021/acs.inorgchem.5b01161
Abstract
Molecular examples of mixed-valence copper complexes through chemical oxidation are rare but invoked in the mechanism of substrate activation, especially oxygen, in copper-containing enzymes. To examine the cooperative chemistry between two metals in close proximity to each other we began studying the reactivity of a dinuclear Cu(I) amidinate complex. The reaction of [(2,6-Me2C6H3N)2C(H)]2Cu2, 1, with I2 in tetrahydrofuran (THF), CH3CN, and toluene affords three new mixed-valence copper complexes [(2,6-Me2C6H3N)2C(H)]2Cu2(μ2-I3)(THF)2, 2, [(2,6-Me2C6H3N)2C(H)]2Cu2(μ2-I) (NCMe)2, 3, and [(2,6-Me2C6H3N)2C(H)]3Cu3(μ3-I)2, 4, respectively. The first two compounds were characterized by UV-vis and electron paramagnetic resonance spectroscopies, and their molecular structure was determined by X-ray crystallography. Both di- and trinuclear mixed-valence intermediates were characterized for the reaction of compound 1 to compound 4, and the molecular structure of 4 was determined by X-ray crystallography. The electronic structure of each of these complexes was also investigated using density functional theory.
Recommended Citation
Lane, Andrew C.; Barnes, Charles L.; Antholine, William E.; Wang, Denan; Fiedler, Adam T.; and Walensky, Justin R., "Di- and Trinuclear Mixed-Valence Copper Amidinate Complexes from Reduction of Iodine" (2015). Chemistry Faculty Research and Publications. 467.
https://epublications.marquette.edu/chem_fac/467
Comments
Accepted version. Inorganic Chemistry, Vol 54, No. 17 (August 8, 2015): 8509-8517. DOI. © 2015 American Chemical Society. Used with permission.