Direct NO Reduction by a Biomimetic Iron(II) Pyrazolate MOF.

A novel metal-organic framework (MOF) containing one-dimensional, Fe2+ chains bridged by dipyrazolate linkers and N,N -dimethylformamide (DMF) ligands has been synthesized. The unusual chain-type metal nodes feature accessible coordination sites on adjacent metal centers, resulting in motifs that are reminiscent of the active sites in non-heme diiron enzymes. The MOF facilitates direct reduction of nitric oxide (NO), producing nearly quantitative yields of nitrous oxide (N2O) and emulating the reactivity of flavodiiron nitric oxide reductases (FNORs). The ferrous form of the MOF can be regenerated via a synthetic cycle involving reduction with cobaltocene (CoCp2) followed by reaction with trimethylsilyl triflate (TMSOTf).