Room Temperature Stable Organocuprate Copper(III) Complex

Abstract

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.