期刊
NATURE COMMUNICATIONS
卷 10, 期 -, 页码 -出版社
NATURE PUBLISHING GROUP
DOI: 10.1038/s41467-019-10357-z
关键词
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资金
- National Natural Science Foundation of China [21771176, U1532128, 21671024, 21702109, 21890722, 11811530637]
- international cooperation fund of CAS
- Hundred Talent Program of CAS
- Natural Science Foundation of Tianjin City [18JCYBJC21400]
- Fundamental Research Funds for the Central Universities (Nankai University) [63191515, 63191523, 63191321]
- US DOE [DE-AC0206CH11357]
- Canadian Light Source
- Strategic Priority Research Program of Chinese Academy of Sciences [XDB28000000]
- LNF
The spin state transition from low spin to high spin upon substrate addition is one of the key steps in cytochrome P450 catalysis. External perturbations such as pH and hydrogen bonding can also trigger the spin state transition of hemes through deprotonated histidine (e.g. Cytochrome c). In this work, we report the isolated 2-methylimidazole Cobalt(II) [Co(TPP) (2-MeHlm)] and [Co(TTP)(2-MeHlm)], and the corresponding 2-methylimidazolate derivatives where the N-H proton of axial 2-MeHlm is removed. Interestingly, various spectroscopies including EPR and XAFS determine a high-spin state (S= 3/2) for the imidazolate derivatives, in contrast to the low-spin state (S=1/2) of all known imidazole analogs. DFT assisted stereoelectronic investigations are applied to understand the metal-ligand interactions, which suggest that the dramatically displaced metal center allowing a promotion e(g)(d(pi)) -> b(1g)(d(x2-y2)) is crucial for the occurrence of the spin state transition.
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