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Antiferromagnetical...
Antiferromagnetically coupled [Fe8S9] cluster catalyzed acetylene reduction in a nitrogenase-like enzyme DCCPCh : Insights from QM/MM calculations
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Liao, Rong-Zhen (författare)
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Zhang, Jing-Xuan (författare)
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Lin, Zhenyang (författare)
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- Siegbahn, Per E. M. (författare)
- Stockholms universitet,Institutionen för organisk kemi
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(creator_code:org_t)
- Elsevier BV, 2021
- 2021
- Engelska.
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Ingår i: Journal of Catalysis. - : Elsevier BV. - 0021-9517 .- 1090-2694. ; 398, s. 67-75
- Relaterad länk:
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https://urn.kb.se/re...
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https://doi.org/10.1...
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Abstract
Ämnesord
Stäng
- QM/MM calculations have been used to elucidate the reaction mechanism of the reduction of acetylene to ethylene catalyzed by a nitrogenase-like enzyme DCCPCh with an unusual [Fe8S9] double-cubane cluster. Various plausible reaction pathways, involving different oxidation states and protonation states of the iron-sulfur cluster, have been analyzed to find the most favorable one. The acetylene substrate bridges to the [Fe8S8] cluster via its triple bond in a μ-(bis-η2) coordination mode. After a proton-coupled electron transfer reduction of the reactant complex, the acetylene reduction may be described to proceed via a special “double-electron transfer induced proton transfer” mechanism, deduced from the principal interacting orbital analysis. The anti-ferromagnetically coupled [Fe8S8] cluster delivers a pair of α- and β-electrons to the substrate, concertedly but asynchronously with a proton transfer mediated by the second-shell Lys147 residue to one of the acetylene carbon atoms. Subsequently, the second proton-coupled electron transfer proceeds, followed by protonation of the substrate to afford the ethylene product. During the two-electron reaction, the oxidation states of the [Fe8S8] cluster cycle from [FeII6FeIII2], to [FeII7FeIII], to [FeII5FeIII3], and back to [FeII6FeIII2].
Ämnesord
- NATURVETENSKAP -- Kemi (hsv//swe)
- NATURAL SCIENCES -- Chemical Sciences (hsv//eng)
Nyckelord
- FeS cluster
- Reaction mechanism
- Enzyme catalysis
- Proton-coupled electron transfer
Publikations- och innehållstyp
- ref (ämneskategori)
- art (ämneskategori)
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