title: Di- and Trinuclear Mixed-Valence Copper Amidinate Complexes from Reduction of Iodine.
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.
authors.affiliation: Department of Chemistry, University of Missouri , 601 S. College Avenue, Columbia, Missouri 65211, United States.
authors.forename: Andrew C
authors.initials: AC
authors.lastname: Lane
authors.affiliation: Department of Chemistry, University of Missouri , 601 S. College Avenue, Columbia, Missouri 65211, United States.
authors.forename: Charles L
authors.initials: CL
authors.lastname: Barnes
authors.affiliation: Department of Biophysics, Medical College of Wisconsin , 8701 Watertown Plank Road, Milwaukee, Wisconsin 53226, United States.
authors.forename: William E
authors.initials: WE
authors.lastname: Antholine
authors.affiliation: Department of Chemistry, Marquette University , 535 North 14th Street, Milwaukee, Wisconsin 53233, United States.
authors.forename: Denan
authors.initials: D
authors.lastname: Wang
authors.affiliation: Department of Chemistry, Marquette University , 535 North 14th Street, Milwaukee, Wisconsin 53233, United States.
authors.forename: Adam T
authors.initials: AT
authors.lastname: Fiedler
authors.affiliation: Department of Chemistry, University of Missouri , 601 S. College Avenue, Columbia, Missouri 65211, United States.
authors.forename: Justin R
authors.initials: JR
authors.lastname: Walensky
mesh_terms: D000578:Amidines / Q000737:chemistry*; D003300:Copper / Q000737:chemistry*; D018360:Crystallography, X-Ray; D007455:Iodine / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D010084:Oxidation-Reduction; D011789:Quantum Theory
chemical_list: D000578:Amidines; D009942:Organometallic Compounds; D003300:Copper; D007455:Iodine