A Structurally Characterized Cu^III Complex Supported by a Bis(anilido) Ligand and Its Oxidative Catalytic Activity

Three copper(II) complexes of the (R,R)-N,N'-bis(3,5-di-tert-butyl-2-aminobenzylidene)-1,2-diaminocyclohexane ligand, namely [Cu(^N L)], [Cu(^N LH)]⁺ and [Cu(^N LH₂ )]²⁺ , were prepared and structurally characterized. In [Cu(^N LH₂ )]²⁺ the copper ion lies in an octahedral geometry with the aniline groups coordinated in equatorial positions. In [Cu(^N L)] the anilines are deprotonated (anilido moieties) and coordinated to an almost square-planar metal ion. Complex [Cu(^N L)] displays two oxidation waves at E_1/2^ox, 1 =-0.14 V and E_1/2^ox, 2 =0.36 V vs. Fc⁺ /Fc in CH₂ Cl₂ . Complex [Cu(^N LH₂ )]²⁺ displays an irreversible oxidation wave at high potential (1.21 V), but shows a readily accessible and reversible metal-centered reduction at E_1/2^red =-0.67 V (Cu^II /Cu^I redox couple). Oxidation of [Cu(^N L)] by AgSbF₆ produces [Cu(^N L)](SbF₆ ), which was isolated as single crystals. X-ray structure analysis discloses a contraction of the coordination sphere by 0.05 Å upon oxidation, supporting a metal-centered process. Complex [Cu(^N L)](SbF₆ ) displays an intense NIR band at 1260 nm corresponding to an anilido-to-copper(III) charge transfer transition. This compound slowly evolves in CH₂ Cl₂ solution towards [Cu(^N LH)](SbF₆ ), which is a copper(II) complex comprised of both anilido and aniline groups coordinated to the metal center. The copper(III) complex [Cu(^N L)](SbF₆ ) is an efficient catalyst for benzyl alcohol oxidation, with 236 TON in 24 h at 298 K, without additives other than oxygen and a base.