期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 143, 期 41, 页码 16943-16959出版社
AMER CHEMICAL SOC
DOI: 10.1021/jacs.1c04919
关键词
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资金
- National Science Foundation [CHE-1900380]
- NRF of Korea through CRI [NRF2021R1A3B1076539]
- Basic Science Research Program [NRF-2020R1I1A1A01074630, NRF-2019R1I1A1A01055822]
- Eastman Research Fellowship
This research reports the preparation, spectroscopic characterization, and reactivity studies of a Co(IV)-oxo complex with an N4-macrocyclic coligand. Experimental data show the formation of a Co(IV) intermediate and the existence of the oxo group, supported by DFT calculations and spectroscopic techniques analyzing the structure.
In this paper, we report the preparation, spectro-scopic and theoretical characterization, and reactivity studies of a Co(IV)-oxo complex bearing an N4-macrocyclic coligand, 12-TBC (12-TBC = 1,4,7,10-tetrabenzyl-1,4,7,10-tetraazacyclododecane). On the basis of the ligand and the structure of the Co(II) precursor, [Co-II(12-TBC)(CF3SO3)(2)], one would assume that this species corresponds to a tetragonal Co(IV)-oxo complex, but the spectroscopic data do not support this notion. Co K-edge XAS data show that the treatment of the Co( II) precursor with iodosylbenzene (PhIO) as an oxidant at -40 degrees C in the presence of a proton source leads to a distinct shift in the Co K-edge, in agreement with the formation of a Co(IV) intermediate. The presence of the oxo group is further demonstrated by resonance Raman (rRaman) spectroscopy. Interestingly, the EPR data of this complex show a high degree of rhombicity, indicating structural distortion. This is further supported by the EXAFS data. Using DFT calculations, a structural model is developed for this complex with a ligand-protonated structure that features a Co = O center dot center dot center dot HN hydrogen bond and a four-coordinate Co center in a seesaw-shaped coordination geometry. Magnetic circular dichroism (MCD) spectroscopy further supports this finding. The hydrogen bond leads to an interesting polarization of the Co-oxo pi-bonds, where one O(p) lone-pair is stabilized and leads to a regular Co(d) interaction, whereas the other pi-bond shows an inverted ligand field. The reactivity of this complex in hydrogen atom and oxygen atom transfer reactions is discussed as well.
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