A Structurally Characterized CuIII Complex Supported by a Bis(anilido) Ligand and Its Oxidative Catalytic Activity.
Amélie KochemJennifer K MolloyGisèle GellonNicolas LeconteChristian PhilouzeFlorian BerthiolOlivier JarjayesFabrice ThomasPublished in: Chemistry (Weinheim an der Bergstrasse, Germany) (2017)
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 E1/2ox, 1 =-0.14 V and E1/2ox, 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 E1/2red =-0.67 V (CuII /CuI 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.