Asset Details
Do you wish to reserve the book?
Proton mediated spin state transition of cobalt heme analogs
Hey, we have placed the reservation for you!
By the way, why not check out events that you can attend while you pick your title.
Oops! Something went wrong.
Looks like we were not able to place the reservation. Kindly try again later.
Are you sure you want to remove the book from the shelf?
Proton mediated spin state transition of cobalt heme analogs
Do you wish to request the book?
Proton mediated spin state transition of cobalt heme analogs
Please be aware that the book you have requested cannot be checked out. If you would like to checkout this book, you can reserve another copy
We have requested the book for you!
Your request is successful and it will be processed during the Library working hours. Please check the status of your request in My Requests.
Oops! Something went wrong.
Looks like we were not able to place your request. Kindly try again later.
Journal Article
Proton mediated spin state transition of cobalt heme analogs
2019
Overview
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
e
g
(d
π
) →
b
1g
(
d
x
2
-
y
2
) is crucial for the occurrence of the spin state transition.
Studying the electronic structures and spin transitions of synthetic heme analogs is crucial to advancing our understanding of heme enzyme mechanisms. Here the authors show that a Co(II) porphyrin complex undergoes an unexpected spin state transition upon deprotonation of its axial imidazole ligand.
Publisher
Nature Publishing Group UK,Nature Publishing Group,Nature Portfolio
