Deciphering the mechanism of O reduction with electronically tunable non-heme iron enzyme model complexes.

A homologous series of electronically tuned 2,2,2-nitrilotris(-arylacetamide) pre-ligands ( ) were prepared (R = NO, CN, CF, F, Cl, Br, Et, Me, H, OMe, NMe) and some of their corresponding Fe and Zn species synthesized. The iron complexes react rapidly with O, the final products of which are diferric mu-oxo bridged species. The crystal structure of the oxidized product obtained from DMA solutions contain a structural motif found in some diiron proteins.

Photochemical Water-Splitting with Organomanganese Complexes.

Certain organometallic chromophores with water-derived ligands, such as the known [Mn(CO)(μ-OH)] (1) tetramer, drew our attention as possible platforms to study water-splitting reactions. Herein, we investigate the UV irradiation of various tricarbonyl organomanganese complexes, including 1, and demonstrate that dihydrogen, CO, and hydrogen peroxide form as products in a photochemical water-splitting decomposition reaction. The organic and manganese-containing side products are also characterized.