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Room Temperature Stable Organocuprate Copper(III) Complex

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journal contribution
posted on 24.06.2013, 00:00 by Steven F. Hannigan, June S. Lum, Jeffrey W. Bacon, Curtis Moore, James A. Golen, Arnold L. Rheingold, Linda H. Doerrer
The paramagnetic trigonal-planar copper complexes {K­(18C6)}­[CuII(OC­(CH3)­(CF3)2)3] (2) and K­[CuII(OC­(C6H5)­(CF3)2)3] (3) have been prepared and characterized, including X-ray crystallography, in 61% and 3% yields, respectively. The latter complex does not form preferentially, because CuBr2 and KOC­(C6H5)­(CF3)2)3 also form the diamagnetic complexes {K­(18C6)}­[K2{CuI(OC­(C6H5)­(CF3)2)2}3] (4) and {K­(18C6)}­[CuIII(OC­(C6H4)­(CF3)2)2] (5). These species were characterized by X-ray crystallography, UV–vis spectroscopy, 1H, 13C­{1H}, and 19F­{1H} NMR spectroscopy, and elemental analysis. The unique organocuprate Cu­(III) species with {O2C2} coordination was formed by ortho metalation of two phenyl rings, resulting in trans-{O2C2} coordination of Cu­(III), and is stable at room temperature in the solid state and in dark solutions of THF.