Direct Reduction of NO to N<sub>2</sub>O by a Mononuclear Nonheme Thiolate Ligated Iron(II) Complex via Formation of a Metastable {FeNO}<sup>7</sup> Complex
Aniruddha Dey, Therese Albert, Richard Y. Kong, Samantha N. MacMillan, Pierre Moënne‐Loccoz, Kyle M. Lancaster, David P. Goldberg
Abstract
Addition of NO to a nonheme dithiolate-ligated iron(II) complex, FeII(Me3TACN)(S2SiMe2) (1), results in the generation of N2O. 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 N2O, providing a rare example of a mononuclear thiolate-ligated {FeNO}7 that mediates NO reduction to N2O without the requirement of any exogenous electron or proton sources.
Topics & Concepts
ChemistryMetastabilityElectron paramagnetic resonanceRaman spectroscopyMössbauer spectroscopyCrystallographyResonance (particle physics)PhotochemistryStereochemistryNuclear magnetic resonanceOrganic chemistryAtomic physicsPhysicsOpticsMetalloenzymes and iron-sulfur proteinsMagnetism in coordination complexesCarbon dioxide utilization in catalysis