Reaction of the noninnocent iminophenol‐iminopyridine hybrid ligand HLIPIP, where LIPIP denotes [2‐((E)‐{(E)‐2‐[(E)‐pyridin‐2‐ylmethyleneamino]benzylidene}amino)‐4,6‐di‐tert‐butylphenolate], with copper acetate afforded a copper complex, LAPIPCuII, in which one of the imine functional groups is oxidized to an amide during metal complexation. The new CuII complex is capable of catalyzing efficient aerobic alcohol oxidation under mild conditions. The crystal structure of LAPIPCuII exhibits a square‐planar geometry with the CuII center coordinated by three nitrogen atoms and one oxygen atom. Electrochemical studies were conducted to evaluate the redox‐active behavior of the complex, and the results showed a quasireversible reduction and a ligand‐based oxidation process. The neutral species of LAPIPCuII is EPR active, which is consistent with a paramagnetic electronic ground state (d9, S = 1/2), whereas the one‐electron oxidized complex was X‐band EPR silent. One‐electron chemical oxidation of LAPIPCuII gave a new species that can be attributed to a CuII‐phenoxyl radical complex. Based on EPR measurements in conjunction with density functional theory calculations, [LAPIPCuII]+ is proposed to have a triplet electronic ground state, exhibiting a weak ferromagnetic interaction between the CuII center and the coordinated phenoxyl radical.
Metal and ligand cooperation provides a driving force for the water-mediated oxidative transformation of imine to amide in copper and nickel complexes versus a zinc analogue.
Structure–reactivity correlation in o-aminophenolate zinc catalysts provides an atom-efficient protocol for the conversion of CO2 into valuable cyclic carbonates.
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