Green, Michael T. (2000) Imidazole-Ligated Compound I Intermediates: The Effects of Hydrogen Bonding. Journal of the American Chemical Society, 122 (39). pp. 9495-9499. ISSN 0002-7863. doi:10.1021/ja994377k. https://resolver.caltech.edu/CaltechAUTHORS:20161018-135415365
Full text is not posted in this repository. Consult Related URLs below.
Use this Persistent URL to link to this item: https://resolver.caltech.edu/CaltechAUTHORS:20161018-135415365
Abstract
An unresolved issue of peroxidase activity is the role played by the hydrogen bond between the proximal histidine ligand and a highly conserved aspartate group. It has been postulated that this hydrogen bond imparts imidazolate character to the axial ligand, increasing its donating ability and stabilizing the high valent compound I intermediate. A general feature of biological compound I intermediates is that they display weaker spin couplings than model systems. To understand how the Asp-His hydrogen bond affects the electronic structure of the compound I intermediate and to establish a connection between it and the decreased coupling strengths observed in peroxidases, we have perfomed density functional calculations on imidazole- and imidazolate-ligated perferryl porphyrin species. It was found that the imidazolate compound I intermediate possesses an imidazolate-based radical, while the imidazole compound I intermediate possesses a porphyrin-based radical. Delocalizaton of the radical onto the axial ligand was found to reduce the strength of the spin coupling.
Item Type: | Article | |||||||||
---|---|---|---|---|---|---|---|---|---|---|
Related URLs: |
| |||||||||
Additional Information: | © 2000 American Chemical Society. Received December 15, 1999. Publication Date (Web): September 16, 2000. The author thanks Harry Gray, the Burroughs Wellcome Fund, and the National Institutes of Health for supporting this research. | |||||||||
Funders: |
| |||||||||
Issue or Number: | 39 | |||||||||
DOI: | 10.1021/ja994377k | |||||||||
Record Number: | CaltechAUTHORS:20161018-135415365 | |||||||||
Persistent URL: | https://resolver.caltech.edu/CaltechAUTHORS:20161018-135415365 | |||||||||
Official Citation: | Imidazole-Ligated Compound I Intermediates: The Effects of Hydrogen Bonding Michael T. Green Journal of the American Chemical Society 2000 122 (39), 9495-9499 DOI: 10.1021/ja994377k | |||||||||
Usage Policy: | No commercial reproduction, distribution, display or performance rights in this work are provided. | |||||||||
ID Code: | 71231 | |||||||||
Collection: | CaltechAUTHORS | |||||||||
Deposited By: | George Porter | |||||||||
Deposited On: | 18 Oct 2016 21:15 | |||||||||
Last Modified: | 11 Nov 2021 04:41 |
Repository Staff Only: item control page