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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(?2-I3)(THF)2, 2, [(2,6-Me2C6H3N)2C(H)]2Cu2(?2-I) (NCMe)2, 3, and [(2,6-Me2C6H3N)2C(H)]3Cu3(?3-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.

SUBMITTER: Lane AC

PROVIDER: S-EPMC4733884 | biostudies-literature | 2015 Sep

REPOSITORIES: biostudies-literature

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Di- and Trinuclear Mixed-Valence Copper Amidinate Complexes from Reduction of Iodine.

Lane Andrew C AC Barnes Charles L CL Antholine William E WE Wang Denan D Fiedler Adam T AT Walensky Justin R JR

Inorganic chemistry 20150807 17

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 complexe ...[more]

PMID: 26252561

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Project description:A trinuclear nickel complex of phenanthrene-9,10-dione dioxime (H2pqd), namely bis-[?2-9,10-bis-(oxido-imino)-phenanthrene]-bis-[?2-10-(oxido-imino)phenanthrene-9-one oxime](phenanthrene-9,10-dione dioxime)trinickel(II) toluene disolvate, [Ni3(C14H8N2O2)2(C14H9N2O2)2(C14H10N2O2)]·2C7H8, has been isolated and its crystal structure determined. This complex features three independent Ni(II) atoms that are arranged in a triangular fashion along with five supporting ligands. There are two square-planar Ni(II) atoms and a third pseudo-octa-hedral Ni(II) atom. While the square-planar Ni(II) atoms are stacked, there are no ligand bridges between them. Each square-planar Ni(II) atom, however, bridges with the pseudo-octa--hedral Ni(II) atom through Ni-N-O-Ni and Ni-O-Ni bonds. A fluorido-bor-ation reaction of the proton-bridged species gave the analogous complex bis-(?2-bis-{[10-(oxido-imino)-9,10-di-hydro-phenanthren-9-yl-idene]amino}di-fluorido-borato)(phenanthrene-9,10-dione dioxime)trinickel(II) dichloromethane trisolvate, [Ni3(C28H16BF2N4O2)4(C14H10N2O2)]·3CH2Cl2, which shows the same binding structure, but features a widened Ni-Ni inter-action between the square-planar Ni(II) atoms. The proton-bridged complex completes the macrocyclic coordination around the square-planar Ni(II) atoms by means of an O-H?O hydrogen bond. Both compounds feature O-H?N hydrogen bonds between the oxime and the N atoms attached to square-planar nickel atom. The nickel units show no direct inter-action with their nearest neighbors in the extended lattice. Two ?-stacking inter-actions between adjacent mol-ecules are found: one with a centroid-centroid distance of 3.886?(2)?Å and the other with a centroid-centroid distance of 4.256?(3)?Å. In the latter case, although not aromatic, the distance to the centroid of the central phenanthrene ring is shorter, with a distance of 3.528?(3)?Å. Toluene mol-ecules occupy the solvent channels that are oriented along the c axis. In the fluorido-boronate structure, the solvent (DCM) was too badly disordered to be modelled, so its contribution was removed using SQUEEZE [Spek (2015 ?). Acta Cryst. C71, 9-18].

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Di- and Trinuclear Mixed-Valence Copper Amidinate Complexes from Reduction of Iodine.

Publications

Di- and Trinuclear Mixed-Valence Copper Amidinate Complexes from Reduction of Iodine.

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