Electrocatalytic reduction of CO to CO and HCO with Zn(II) complexes displaying cooperative ligand reduction.

Air-stable zinc(II) pyridyl phosphine complexes, [Zn(κ-2,6-{PhPNMe}(NCH))Br] (1) and [Zn(κ-2-{PhPNMe}(NCH))Br] (2) are reported and 1 was capable of electrocatalytic reduction of CO at -2.3 V Fc to yield CO/HCOH in mixed water/acetonitrile solutions. DFT computations support a proposed mechanism involving electron transfer reactions from a species with the anionic PNP ligand ("L/Zn(II)").