TY - JOUR
T1 - Conversion of a Fleeting Open-Shell Iron Nitride into an Iron Nitrosyl
AU - Chang, Hao Ching
AU - Lin, Yen Hao
AU - Werlé, Christophe
AU - Neese, Frank
AU - Lee, Way Zen
AU - Bill, Eckhard
AU - Ye, Shengfa
N1 - Funding Information:
We gratefully acknowledge the financial support from the Max-Planck Society, in particular, the Joint Work Space of MPI-CEC and MPI-KOFO, and the Ministry of Science and Technology of Taiwan (MOST 105-2113-M-003-005-MY3 to W.-Z.L.). W.-Z.L. and S.Y. also acknowledge the MOST-DAAD Project-Based Personnel Exchange Program (MOST 107-2911-I-003-502 and DAAD 57320810).
Publisher Copyright:
© 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.
PY - 2019/12/2
Y1 - 2019/12/2
N2 - 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, [FeVN(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.
AB - 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, [FeVN(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.
KW - EPR spectroscopy
KW - Mössbauer spectroscopy
KW - iron
KW - nitrides
KW - nitrosyl
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U2 - 10.1002/anie.201908689
DO - 10.1002/anie.201908689
M3 - Article
C2 - 31532866
AN - SCOPUS:85074605348
SN - 1433-7851
VL - 58
SP - 17589
EP - 17593
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
IS - 49
ER -