Di- and Trinuclear Mixed-Valence Copper Amidinate Complexes from Reduction of Iodine. Inorg Chem 2015 Sep 08;54(17):8509-17
Date
08/08/2015Pubmed ID
26252561Pubmed Central ID
PMC4733884DOI
10.1021/acs.inorgchem.5b01161Scopus ID
2-s2.0-84941283427 (requires institutional sign-in at Scopus site) 12 CitationsAbstract
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.
Author List
Lane AC, Barnes CL, Antholine WE, Wang D, Fiedler AT, Walensky JRMESH terms used to index this publication - Major topics in bold
AmidinesCopper
Crystallography, X-Ray
Iodine
Models, Molecular
Molecular Structure
Organometallic Compounds
Oxidation-Reduction
Quantum Theory
