Controlling product selectivity during dioxygen reduction with Mn complexes using pendent proton donor relays and added base.

The catalytic reduction of dioxygen (O) is important in biological energy conversion and alternative energy applications. In comparison to Fe- and Co-based systems, examples of catalytic O reduction by homogeneous Mn-based systems is relatively sparse. Motivated by this lack of knowledge, two Mn-based catalysts for the oxygen reduction reaction (ORR) containing a bipyridine-based non-porphyrinic ligand framework have been developed to evaluate how pendent proton donor relays alter activity and selectivity for the ORR, where Mn(dhbpy)Cl (1) was used as a control complex and Mn(dhbpy)Cl (2) contains a pendent -OMe group in the secondary coordination sphere. Using an ammonium-based proton source, ,'-diisopropylethylammonium hexafluorophosphate, we analyzed catalytic activity for the ORR: 1 was found to be 64% selective for HO and 2 is quantitative for HO, with O binding to the reduced Mn(ii) center being the rate-determining step. Upon addition of the conjugate base, ,'-diisopropylethylamine, the observed catalytic selectivity of both 1 and 2 shifted to HO as the primary product. Interestingly, while the shift in selectivity suggests a change in mechanism for both 1 and 2, the catalytic activity of 2 is substantially enhanced in the presence of base and the rate-determining step becomes the bimetallic cleavage of the O-O bond in a Mn-hydroperoxo species. These data suggest that the introduction of pendent relay moieties can improve selectivity for HO at the expense of diminished reaction rates from strong hydrogen bonding interactions. Further, although catalytic rate enhancements are observed with a change in product selectivity when base is added to buffer proton activity, the pendent relays stabilize dimer intermediates, limiting the maximum rate.