Lewis acid-induced change from four- to two-electron reduction of dioxygen catalyzed by copper complexes using scandium triflate.

ABSTRACT: Mononuclear copper complexes, [(tmpa)Cu(II)(CH3CN)](ClO4)2 (1, tmpa = tris(2-pyridylmethyl)amine) and [(BzQ)Cu(II)(H2O)2](ClO4)2 (2, BzQ = bis(2-quinolinylmethyl)benzylamine)], act as efficient catalysts for the selective two-electron reduction of O2 by ferrocene derivatives in the presence of scandium triflate (Sc(OTf)3) in acetone, whereas 1 catalyzes the four-electron reduction of O2 by the same reductant in the presence of Brønsted acids such as triflic acid. Following formation of the peroxo-bridged dicopper(II) complex [(tmpa)Cu(II)(O2)Cu(II)(tmpa)](2+), the two-electron reduced product of O2 with Sc(3+) is observed to be scandium peroxide ([Sc(III)(O2(2-))](+)). In the presence of 3 equiv of hexamethylphosphoric triamide (HMPA), [Sc(III)(O2(2-))](+) was oxidized by [Fe(bpy)3](3+) (b

SUBMITTER: Kakuda S 

PROVIDER: S-EPMC4630010 | biostudies-literature | 2015 Mar

REPOSITORIES: biostudies-literature