Room Temperature Stable Organocuprate Copper(III)
Complex
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Abstract
The paramagnetic trigonal-planar
copper complexes {K(18C6)}[Cu<sup>II</sup>(OC(CH<sub>3</sub>)(CF<sub>3</sub>)<sub>2</sub>)<sub>3</sub>] (<b>2</b>) and K[Cu<sup>II</sup>(OC(C<sub>6</sub>H<sub>5</sub>)(CF<sub>3</sub>)<sub>2</sub>)<sub>3</sub>] (<b>3</b>) have
been prepared and characterized, including X-ray crystallography,
in 61% and 3% yields, respectively. The latter complex does not form
preferentially, because CuBr<sub>2</sub> and KOC(C<sub>6</sub>H<sub>5</sub>)(CF<sub>3</sub>)<sub>2</sub>)<sub>3</sub> also form the diamagnetic
complexes {K(18C6)}[K<sub>2</sub>{Cu<sup>I</sup>(OC(C<sub>6</sub>H<sub>5</sub>)(CF<sub>3</sub>)<sub>2</sub>)<sub>2</sub>}<sub>3</sub>] (<b>4</b>) and {K(18C6)}[Cu<sup>III</sup>(OC(C<sub>6</sub>H<sub>4</sub>)(CF<sub>3</sub>)<sub>2</sub>)<sub>2</sub>] (<b>5</b>). These
species were characterized by X-ray crystallography, UV–vis
spectroscopy, <sup>1</sup>H, <sup>13</sup>C{<sup>1</sup>H}, and <sup>19</sup>F{<sup>1</sup>H} NMR spectroscopy, and elemental analysis.
The unique organocuprate Cu(III) species with {O<sub>2</sub>C<sub>2</sub>} coordination was formed by ortho metalation of two phenyl
rings, resulting in <i>trans</i>-{O<sub>2</sub>C<sub>2</sub>} coordination of Cu(III), and is stable at room temperature in the
solid state and in dark solutions of THF
