Academic Journal
A New Thiolate‐Bound Dimanganese Cluster as a Structural and Functional Model for Class Ib Ribonucleotide Reductases
| العنوان: | A New Thiolate‐Bound Dimanganese Cluster as a Structural and Functional Model for Class Ib Ribonucleotide Reductases |
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| المؤلفون: | Battistella, Beatrice, Lohmiller, Thomas, Cula, Beatrice, Hildebrandt, Peter, Kuhlmann, Uwe, Dau, Holger, Mebs, Stefan, Ray, Kallol |
| بيانات النشر: | Humboldt-Universität zu Berlin |
| سنة النشر: | 2023 |
| المجموعة: | Open-Access-Publikationsserver der Humboldt-Universität: edoc-Server |
| مصطلحات موضوعية: | Bioinorganic Chemistry, Dimanganese Cofactor, Enzyme Models, Phenol Oxidation, Ribonucleotide Reductases, 540 Chemie und zugeordnete Wissenschaften, ddc:540 |
| الوصف: | In class Ib ribonucleotide reductases (RNRs) a dimanganese(II) cluster activates superoxide (O2⋅−) rather than dioxygen (O2), to access a high valent MnIII−O2−MnIV species, responsible for the oxidation of tyrosine to tyrosyl radical. In a biomimetic approach, we report the synthesis of a thiolate‐bound dimanganese complex [MnII2(BPMT)(OAc)2](ClO)4 (BPMT=(2,6‐bis{[bis(2‐pyridylmethyl)amino]methyl}‐4‐methylthiophenolate) (1) and its reaction with O2⋅− to form a [(BPMT)MnO2Mn]2+ complex 2. Resonance Raman investigation revealed the presence of an O−O bond in 2, while EPR analysis displayed a 16‐line St=1/2 signal at g=2 typically associated with a MnIIIMnIV core, as detected in class Ib RNRs. Unlike all other previously reported Mn−O2−Mn complexes, generated by O2⋅− activation at Mn2 centers, 2 proved to be a capable electrophilic oxidant in aldehyde deformylation and phenol oxidation reactions, rendering it one of the best structural and functional models for class Ib RNRs. ; Peer Reviewed |
| نوع الوثيقة: | article in journal/newspaper |
| وصف الملف: | application/pdf |
| اللغة: | English |
| تدمد: | 1521-3773 |
| Relation: | http://edoc.hu-berlin.de/18452/27189; urn:nbn:de:kobv:11-110-18452/27189-5; http://dx.doi.org/10.18452/26506 |
| DOI: | 10.1002/anie.202217076 |
| DOI: | 10.18452/26506 |
| الاتاحة: | http://edoc.hu-berlin.de/18452/27189 https://nbn-resolving.org/urn:nbn:de:kobv:11-110-18452/27189-5 https://doi.org/10.1002/anie.202217076 https://doi.org/10.18452/26506 |
| Rights: | (CC BY-NC 4.0) Attribution-NonCommercial 4.0 International ; https://creativecommons.org/licenses/by-nc/4.0/ |
| رقم الانضمام: | edsbas.C3126A30 |
| قاعدة البيانات: | BASE |
| تدمد: | 15213773 |
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| DOI: | 10.1002/anie.202217076 |