Distorted copper(ii) radicals with sterically hindered salens: electronic structure and aerobic oxidation of alcohols

The sterically hindered salen ligands featuring biphenyl and tetramethyl putrescine linkers were synthesized and chelated to copper. The resulting complexes CuL^bp,tBu, CuL^bp,OMe, CuL^pu,tBu and CuL^pu,OMe were structurally characterized, showing a significanty tetrahedrally distorted metal center. The complexes show two reversible oxidation waves in the range 0.2 to 0.8 V vs. Fc⁺/Fc. A further reduction wave is detected in the range -1.4 to -1.7 V vs. Fc⁺/Fc. It is reversible for CuL^bp,tBu and CuL^bp,OMe and assigned to the Cu^II/Cu^I redox couple. One-electron oxidation of CuL^bp,OMe, CuL^pu,tBu and CuL^pu,OMe was performed chemically and electrochemically. It is accompanied by a quenching of the EPR resonances. Phenoxyl radical formation was established by X-Ray diffraction on the cations [CuL^bp,OMe]⁺ and [CuL^pu,OMe]⁺, whereby the coordination sphere is elongated upon oxidation with quinoidal distributions of bond distances. The cations exhibit a NIR band of moderate intensity in their optical spectrum, supporting their classification as class II mixed-valent radical species according to the Robin Day classification. The proposed electronic structures are supported by DFT calculations. The cations [CuL^bp,OMe]⁺, [CuL^pu,tBu]⁺ and [CuL^pu,OMe]⁺ were active towards aerobic oxidation of the unactivated alcohol 2-phenylethanol, with TON numbers up to 58 within 3 h.