Abstract
Addition of NO to a nonheme dithiolate-ligated iron(II) complex, Fe(II)(Me(3)TACN)(S(2)SiMe(2)) (1), results in the generation of N(2)O. Low-temperature spectroscopic studies reveal a metastable six-coordinate {FeNO}(7) intermediate (S = 3/2) that was trapped at -135 °C and was characterized by low-temperature UV-vis, resonance Raman, EPR, Mössbauer, XAS, and DFT studies. Thermal decay of the {FeNO}(7) species leads to the evolution of N(2)O, providing a rare example of a mononuclear thiolate-ligated {FeNO}(7) that mediates NO reduction to N(2)O without the requirement of any exogenous electron or proton sources.