EPR spectroscopy elucidates the electronic structure of [Fe-V(O)(TAML)] complexes
- 주제(기타) Chemistry, Inorganic & Nuclear
- 설명문(일반) [Kim, Yujeong; Kim, Sun Hee] Korea Basic Sci Inst KBSI, Western Seoul Ctr, Seoul 03759, South Korea; [Kim, Yujeong; Nguyen, Linh K.; Lee, Yong-Min; Nam, Wonwoo; Kim, Sun Hee] Ewha Womans Univ, Dept Chem & Nano Sci, Seoul 03760, South Korea; [Kim, Jin] Sunchon Natl Univ, Dept Chem, Sunchon 57922, South Korea
- 등재 SCIE, SCOPUS
- 발행기관 ROYAL SOC CHEMISTRY
- 발행년도 2021
- 총서유형 Journal
- URI http://www.dcollection.net/handler/ewha/000000182347
- 본문언어 영어
- Published As http://dx.doi.org/10.1039/d1qi00522g
초록/요약
Multifrequency, multitechnique pulse EPR spectroscopy was employed to unravel the spin Hamiltonian parameters of O-17 in the [Fe-V 00000000 00000000 00000000 00000000 11111111 00000000 11111111 00000000 00000000 00000000 O] moiety with two different tetraamido macrocyclic ligands (TAMLs), [Fe-V(O)(TAML-1)](-) (1, H-4(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 [Fe-V(O)(TAML-2)](-) (2, H-4(TAML-2) = H-4[(Me2CNCOCMe2NCO)(2)CMe2]), to investigate the electronic structure of Fe-V-oxo species. Although rigorous computational studies on high-valent iron-oxo species have been reported recently, experimental evidence to explicate the electronic structure of Fe-V-oxo species is sparse. In particular, a complete hyperfine tensor of O-17 can hardly be detected. Herein, we successfully probed the hyperfine tensor of O-17 of the Fe-V-oxo moiety using ENDOR spectroscopy. Hence, the EPR spectroscopic results reported here provide a conclusive experimental basis for elucidating the electronic structure of the Fe-V-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.
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