Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 138, Issue 20, Pages 6484-6491Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jacs.6b00802
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Funding
- Office of Science, Basic Energy Sciences of the U.S. Department of Energy [DE-AC02-05CH11231, DE-FG02-07ER15903]
- National Institutes of Health [S10-RR027172, SRR023679A, 1S10RR016634-01]
- Joint Center for Artificial Photosynthesis, a U.S. Department of Energy, Office of Science, Basic Energy Sciences Innovation Hub [DE-SC0004993]
- National Science Foundation (NSF) [DGE 1106400]
- Philomathia Graduate Student Fellowship in the Environmental Sciences
- NSF
- U.S. Department of Energy (DOE) [DE-FG02-07ER15903] Funding Source: U.S. Department of Energy (DOE)
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The synthesis of discrete, cationic binuclear mu-aryl dicopper complexes [Cu-2(mu-eta(1):eta(1)-Ar)DPFN]X (Ar = C6H5, 3,5-(CF3)(2)C6H3, and C6F5; DPFN = 2,7-bis(fluoro-di(2-pyridy1)methyl)-1,8-naphthyridine; X = BAr4- and NTf2-; Tf = SO2CF3) was achieved by treatment of a dicopper complex [Cu-2(mu-eta(1):eta(1)-NCCH3)DPFN]X-2 (X = PF6- and NTf2-) with tetraarylborates. Structural characterization revealed symmetrically bridging aryl groups, and H-1 NMR spectroscopy evidenced the same structure in solution at 24 degrees C. Electrochemical investigation of the resulting arylcopper complexes uncovered reversible redox events that led to the synthesis and isolation of a rare mixed-valence organocopper complex [Cu-2(mu-eta(1):eta(1)--Ph)DPFN](NTf2)(2) in high yield. The solid-state structure of the mixed-valence mu-phenyl complex exhibits inequivalent copper centers, despite a short Cu center dot center dot center dot Cu distance. Electronic and variable-temperature electron paramagnetic resonance spectroscopy of the mixed-valence mu-phenyl complex suggest that the degree of spin localization is temperature-dependent, with a high degree of spin localization observed at lower temperatures. Electronic structure calculations agree with the experimental results and suggest that the spin is localized almost entirely on one metal center.
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