Conversion of a Fleeting Open‐Shell Iron Nitride into an Iron Nitrosyl
Open Access
- 18 September 2019
- journal article
- research article
- Published by Wiley in Angewandte Chemie
- Vol. 58 (49), 17589-17593
- https://doi.org/10.1002/anie.201908689
Abstract
Terminal metal nitrides have been proposed as key intermediates in a series of pivotal chemical transformations. However, exploring the chemical activity of transient tetragonal iron(V)‐nitrides is largely impeded by their facile dimerization in fluid solutions. Herein, we present in situ EPR and Mössbauer investigations of unprecedented oxygenation of a paramagnetic iron(V)‐nitrido intermediate, [Fe V N(cyclam‐ac)] + ( 2 , cyclam‐ac – = 1,4,8,11‐tetraazacyclotetradecane‐1‐acetate anion), yielding an iron‐nitrosyl complex, [Fe(NO)(cyclam‐ac)] + ( 3 ). Further theoretical studies suggest that during the reaction a closed‐shell singlet O atom is transferred to 2 . Consequently, the N‐O bond formation does not follow a radical coupling mechanism proposed for the N‐N bond formation, but is accomplished by three mutual electron‐transfer pathways between 2 and the O atom donor, thanks to the ambiphilic nature of 2 .Funding Information
- Max-Planck-Gesellschaft
This publication has 47 references indexed in Scilit:
- ME and ME complexes of iron and cobalt that emphasize three-fold symmetry (E=O, N, NR)Coordination Chemistry Reviews, 2011
- Ammonia oxidation on Ir(111): Why Ir is more selective to N2 than PtCatalysis Today, 2010
- Isolation and Hydrogenation of a Complex with a Terminal Iridium–Nitrido BondAngewandte Chemie, 2009
- TERMINAL NITRIDO AND IMIDO COMPLEXES OF THE LATE TRANSITION METALSComments on Inorganic Chemistry, 2009
- Reactions at Surfaces: From Atoms to Complexity (Nobel Lecture)Angewandte Chemie, 2008
- Radical (NO) and Nonradical (N2O) Reagents Convert a Ruthenium(IV) Nitride to the Same Nitrosyl ComplexInorganic Chemistry, 2007
- Electrophilic Ruthenium(VI) Nitrido Complex Containing Kläui's Oxygen Tripodal LigandInorganic Chemistry, 2007
- The Geometric and Electronic Structure of [(cyclam‐acetato)Fe(N)]+: A Genuine Iron(V) Species with a Ground‐State Spin S=1/2Angewandte Chemie, 2005
- The Geometric and Electronic Structure of [(cyclam‐acetato)Fe(N)]+: A Genuine Iron(V) Species with a Ground‐State Spin S=1/2Angewandte Chemie, 2005
- A Tetrahedrally Coordinated L3Fe−Nx Platform that Accommodates Terminal Nitride (FeIV⋮N) and Dinitrogen (FeI−N2−FeI) LigandsJournal of the American Chemical Society, 2004