Multifrequency,multitechnique pulse EPR spectroscopy was employed to unravel the spin Hamiltonian parameters of^(17)O in the[Fe^(Ⅴ)=O]moiety with two different tetraamido macrocyclic ligands(TAMLs),[Fe^(Ⅴ)(O)(TAML-1...Multifrequency,multitechnique pulse EPR spectroscopy was employed to unravel the spin Hamiltonian parameters of^(17)O in the[Fe^(Ⅴ)=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)[(Me_(2)CNCOCMe_(2)NCO)_(2)CMe_(2)]),to investigate the electronic structure of Fe^(Ⅴ)-oxo species.Although rigorous computational studies on highvalent 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^(17)O can hardly be detected.Herein,we successfully probed the hyperfine tensor of^(17)O 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.展开更多
国际理论与应用力学联合会（International Union of Theoretical and Applied Mechanics，IU—TAMl是国际力学界最具权威的非政府学术组织，是国际科学理事会（International CouncilforSci．ence，ICSU；国科联）的国际科学联合会成员...国际理论与应用力学联合会（International Union of Theoretical and Applied Mechanics，IU—TAMl是国际力学界最具权威的非政府学术组织，是国际科学理事会（International CouncilforSci．ence，ICSU；国科联）的国际科学联合会成员（Scientific Union）．国际理论与应用力学联合会的会员（Adhering Organization）由代表国家级的相关组织或学会组成．经国务院和中国科协批准，1980年中国力学学会正式向IUTAM提出申请，并被IUTAM接纳成为该组织的国家会员．展开更多
基金supported by the National Research Foundation of Korea(NRF-2017M3D1A1039380 and NRF-2020R1F1A1069151)KBSI grant C1300000 to S.H.K+1 种基金supported by the NRF of Korea through CRI(NRF-2012R1A3A2048842 to W.N.)the Basic Science Research Program(NRF-2020R1I1A1A01074630 to Y.-M.L.).
文摘Multifrequency,multitechnique pulse EPR spectroscopy was employed to unravel the spin Hamiltonian parameters of^(17)O in the[Fe^(Ⅴ)=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)[(Me_(2)CNCOCMe_(2)NCO)_(2)CMe_(2)]),to investigate the electronic structure of Fe^(Ⅴ)-oxo species.Although rigorous computational studies on highvalent 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^(17)O can hardly be detected.Herein,we successfully probed the hyperfine tensor of^(17)O 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.
文摘国际理论与应用力学联合会（International Union of Theoretical and Applied Mechanics，IU—TAMl是国际力学界最具权威的非政府学术组织，是国际科学理事会（International CouncilforSci．ence，ICSU；国科联）的国际科学联合会成员（Scientific Union）．国际理论与应用力学联合会的会员（Adhering Organization）由代表国家级的相关组织或学会组成．经国务院和中国科协批准，1980年中国力学学会正式向IUTAM提出申请，并被IUTAM接纳成为该组织的国家会员．
