Abstract
Multifrequency, multitechnique pulse EPR spectroscopy was employed to unravel the spin Hamiltonian parameters of 17O in the [FeVO] moiety with two different tetraamido macrocyclic ligands (TAMLs), [FeV(O)(TAML-1)]- (1, H4(TAML-1) = 3,4,8,9-tetrahydro-3,3,6,6,9-hexamethyl-1H-1,4,8,11-benzotetraazocyclotridecane-2,5,7,10-(6H,11H)-tetrone) and [FeV(O)(TAML-2)]- (2, H4(TAML-2) = H4[(Me2CNCOCMe2NCO)2CMe2]), to investigate the electronic structure of FeV-oxo species. Although rigorous computational studies on high-valent iron-oxo species have been reported recently, experimental evidence to explicate the electronic structure of FeV-oxo species is sparse. In particular, a complete hyperfine tensor of 17O can hardly be detected. Herein, we successfully probed the hyperfine tensor of 17O of the FeV-oxo moiety using ENDOR spectroscopy. Hence, the EPR spectroscopic results reported here provide a conclusive experimental basis for elucidating the electronic structure of the FeV-oxo complex. Moreover, the reactivity of the two different complexes is very distinct, and our results may provide insight into how their electronic structure contributes to their reactivity.
Original language | English |
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Pages (from-to) | 3775-3783 |
Number of pages | 9 |
Journal | Inorganic Chemistry Frontiers |
Volume | 8 |
Issue number | 15 |
DOIs | |
State | Published - 7 Aug 2021 |
Bibliographical note
Funding Information:This work was supported by the National Research Foundation of Korea (NRF-2017M3D1A1039380 and NRF-2020R1F1A1069151) and KBSI grant C1300000 to S. H. K. This work was also supported by the NRF of Korea through CRI (NRF-2012R1A3A2048842 to W. N.) and the Basic Science Research Program (NRF-2020R1I1A1A01074630 to Y.-M. L.).
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