Guchhait, Tapas ; Sarkar, Sabyasachi ; Pandit, Younis Ahmad ; Rath, Sankar Prasad (2017) Probing Bis‐FeIVMauG: Isolation of Highly Reactive Radical Intermediates Chemistry - A European Journal, 23 (43). pp. 10270-10275. ISSN 0947-6539
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Official URL: http://doi.org/10.1002/chem.201702321
Related URL: http://dx.doi.org/10.1002/chem.201702321
Abstract
MauG is a diheme enzyme that utilizes two covalently bound c-type heme centers. We report here step-wise oxidations of a synthetic analogue of MauG in which two heme centers are bridged covalently through a flexible linker containing a pyrrole moiety. One- and two-electron oxidations produce monocation radical and dication diradical intermediates, respectively, which, being highly reactive, undergo spontaneous intramolecular rearrangement involving the pyrrole bridge itself to form indolizinium-fused chlorin–porphyrin and spiro–porphyrinato heterodimers. Unlike in MauG, where the two oxidizing equivalents produce the bis-FeIV redox state, the synthetic analogue of the same, however, stabilizes two ferric hemes, each coupled with a porphyrin π-cation radical. The present study highlights the possible role played by the bridge in the electronic communication.
Item Type: | Article |
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Source: | Copyright of this article belongs to John Wiley and Sons, Inc. |
ID Code: | 120839 |
Deposited On: | 06 Jul 2021 06:28 |
Last Modified: | 06 Jul 2021 06:28 |
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