Proton mediated spin state transition of cobalt heme analogs

Jianping Zhao, Qian Peng, Zijian Wang, Wei Xu, Hongyan Xiao, Qi Wu, Hao-Ling Sun, Fang Ma, Jiyong Zhao, Cheng-Jun Sun, Jianzhang Zhao and Jianfeng Li ()
Additional contact information
Jianping Zhao: University of Chinese Academy of Sciences, Yanqi Lake, Huairou District
Qian Peng: Nankai University
Zijian Wang: Nankai University
Wei Xu: Chinese Academy of Sciences
Hongyan Xiao: Chinese Academy of Sciences
Qi Wu: University of Chinese Academy of Sciences, Yanqi Lake, Huairou District
Hao-Ling Sun: Beijing Normal University
Fang Ma: Beijing Normal University
Jiyong Zhao: Argonne National Laboratory
Cheng-Jun Sun: Argonne National Laboratory
Jianzhang Zhao: Dalian University of Technology
Jianfeng Li: University of Chinese Academy of Sciences, Yanqi Lake, Huairou District

Nature Communications, 2019, vol. 10, issue 1, 1-8

Abstract: Abstract 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-MeHIm)] and [Co(TTP)(2-MeHIm)], and the corresponding 2-methylimidazolate derivatives where the N−H proton of axial 2-MeHIm 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 eg(dπ) → b1g( $$d_{x^2 - y^2}$$ d x 2 - y 2 ) is crucial for the occurrence of the spin state transition.

Date: 2019
References: Add references at CitEc
Citations:

Downloads: (external link)
https://www.nature.com/articles/s41467-019-10357-z Abstract (text/html)

Related works:
This item may be available elsewhere in EconPapers: Search for items with the same title.

Export reference: BibTeX RIS (EndNote, ProCite, RefMan) HTML/Text

Persistent link: https://EconPapers.repec.org/RePEc:nat:natcom:v:10:y:2019:i:1:d:10.1038_s41467-019-10357-z

Ordering information: This journal article can be ordered from
https://www.nature.com/ncomms/

DOI: 10.1038/s41467-019-10357-z

Access Statistics for this article

Nature Communications is currently edited by Nathalie Le Bot, Enda Bergin and Fiona Gillespie

More articles in Nature Communications from Nature
Bibliographic data for series maintained by Sonal Shukla () and Springer Nature Abstracting and Indexing ().