Premium
Conversion of a Fleeting Open‐Shell Iron Nitride into an Iron Nitrosyl
Author(s) -
Chang HaoChing,
Lin YenHao,
Werlé Christophe,
Neese Frank,
Lee WayZen,
Bill Eckhard,
Ye Shengfa
Publication year - 2019
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201908689
Subject(s) - cyclam , chemistry , nitride , electron transfer , electron paramagnetic resonance , metal , crystallography , tetragonal crystal system , photochemistry , inorganic chemistry , crystal structure , organic chemistry , nuclear magnetic resonance , physics , layer (electronics)
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, in situ EPR and Mössbauer investigations are presented 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 .