New Cu(I) complexes with biquinolyl-containing polymer ligands as electrocatalysts for O2 activation in the oxidation of alcohols

Electrochemical Formation of the Redox-Active Metal-Containing Polymers for Catalytic and Electrocatalytic Applications

“…0.30 V vs. Ag/AgCl/KCl. In both cases rate determining step is α-H-atom transfer, the activation energies are similar (9,12). Evidently, we obtained an example of functional modeling of enzymatic process.…”

“…In our previous publications we showed that these polymers can be converted to redox-active metal -containing polymer complexes using sacrificial anodes as a source of Cu(I) (9) and Pd(II) (10) ions. The obtained Cupolymer complexes exhibit excellent efficiency in aerobic electrocatalytic oxidation of aliphatic alcohols (9) and amines (11) to carbonyl compounds.…”

“…In our previous publications we showed that these polymers can be converted to redox-active metal -containing polymer complexes using sacrificial anodes as a source of Cu(I) (9) and Pd(II) (10) ions. The obtained Cupolymer complexes exhibit excellent efficiency in aerobic electrocatalytic oxidation of aliphatic alcohols (9) and amines (11) to carbonyl compounds. DFT investigation of the reaction mechanism (12) revealed some similarities with the natural catalytic cycle performed by Cu containing enzyme Galactose Oxidase and allowed to conclude that we have an example of functional modeling of enzymatic process, with the electrode used as a redox cofactor and the polymer ligand maintaining the coordination polyhedra of the active center optimal for catalysis.…”

Synthesis of heteropolynuclear CuI and PdII complexes with polymeric 2,2′-biquinoline-containing ligands and investigation of their catalytic activity in the Sonogashira couplings

“…2). 11 The variation of the Pd II : Cu I : biQ molar ratio showed that approximately equal amounts of Pd II and Cu I ions and a three to four fold excess of the total number of biQ fragments of the initial polymer are optimal for catalytic reactions.…”

“…Pre viously, it was found 13 that Pd II coordination to the biQ fragments of a polymer chain gives rise to an intense peak at -0.45 V (vs. Ag/AgCl/KCl) in the voltammogram, which corresponds to the Pd II /Pd 0 transition, indicating the formation of biQPdL 2 (L is the solvent molecule, for example, NMP). The complexation with Cu I ions was detected by appearance of peaks at 0.44 and 0.69 V (vs. Ag/AgCl/KCl) corresponding to the Cu I /Cu II redox transition accompanying the formation of coordination units with one or two biQ ligands in the copper coordina tion sphere, biQCu I L 2 and (biQ) 2 Cu I , respectively (see Refs 10,11,12). Figure 1 shows the CV curve recorded for the heteropolynuclear complex containing Cu I and Pd II ions coordinated to the polymeric ligand PA II in the molar ratio Cu : Pd : biQ = 1 : 1 : 4.…”