A Gas-Phase Ca n Mn 4-n O 4 + Cluster Model for the Oxygen-Evolving Complex of Photosystem II
One of the fundamental processes in nature, the oxidation of water, is catalyzed by a small CaMn O ⋅MnO cluster located in photosystem II (PS II). Now, the first successful preparation of a series of isolated ligand-free tetrameric Ca Mn O (n=0-4) cluster ions is reported, which are employed as stru...
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| Veröffentlicht in: | Angewandte Chemie International Edition 2019-06, Vol.58 (25), p.8504-8509 |
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| creator | Mauthe, Silvia Fleischer, Irene Bernhardt, Thorsten M Lang, Sandra M Barnett, Robert N Landman, Uzi |
| description | One of the fundamental processes in nature, the oxidation of water, is catalyzed by a small CaMn
O
⋅MnO cluster located in photosystem II (PS II). Now, the first successful preparation of a series of isolated ligand-free tetrameric Ca
Mn
O
(n=0-4) cluster ions is reported, which are employed as structural models for the catalytically active site of PS II. Gas-phase reactivity experiments with D
O and H
O in an ion trap reveal the facile deprotonation of multiple water molecules via hydroxylation of the cluster oxo bridges for all investigated clusters. However, only the mono-calcium cluster CaMn
O
is observed to oxidize water via elimination of hydrogen peroxide. First-principles density functional theory (DFT) calculations elucidate mechanistic details of the deprotonation and oxidation reactions mediated by CaMn
O
as well as the role of calcium. |
| doi_str_mv | 10.1002/anie.201903738 |
| format | Article |
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O
⋅MnO cluster located in photosystem II (PS II). Now, the first successful preparation of a series of isolated ligand-free tetrameric Ca
Mn
O
(n=0-4) cluster ions is reported, which are employed as structural models for the catalytically active site of PS II. Gas-phase reactivity experiments with D
O and H
O in an ion trap reveal the facile deprotonation of multiple water molecules via hydroxylation of the cluster oxo bridges for all investigated clusters. However, only the mono-calcium cluster CaMn
O
is observed to oxidize water via elimination of hydrogen peroxide. First-principles density functional theory (DFT) calculations elucidate mechanistic details of the deprotonation and oxidation reactions mediated by CaMn
O
as well as the role of calcium.</description><identifier>ISSN: 1433-7851</identifier><identifier>EISSN: 1521-3773</identifier><identifier>DOI: 10.1002/anie.201903738</identifier><identifier>PMID: 30985054</identifier><language>eng</language><publisher>Germany</publisher><ispartof>Angewandte Chemie International Edition, 2019-06, Vol.58 (25), p.8504-8509</ispartof><rights>2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c1074-4cbaed2945379be4bb0b0f984a6fad20a022f2a744778b5564c293f4bc97071c3</citedby><cites>FETCH-LOGICAL-c1074-4cbaed2945379be4bb0b0f984a6fad20a022f2a744778b5564c293f4bc97071c3</cites><orcidid>0000-0001-7851-0850 ; 0000-0002-1586-1554</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,780,784,27924,27925</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/30985054$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Mauthe, Silvia</creatorcontrib><creatorcontrib>Fleischer, Irene</creatorcontrib><creatorcontrib>Bernhardt, Thorsten M</creatorcontrib><creatorcontrib>Lang, Sandra M</creatorcontrib><creatorcontrib>Barnett, Robert N</creatorcontrib><creatorcontrib>Landman, Uzi</creatorcontrib><title>A Gas-Phase Ca n Mn 4-n O 4 + Cluster Model for the Oxygen-Evolving Complex of Photosystem II</title><title>Angewandte Chemie International Edition</title><addtitle>Angew Chem Int Ed Engl</addtitle><description>One of the fundamental processes in nature, the oxidation of water, is catalyzed by a small CaMn
O
⋅MnO cluster located in photosystem II (PS II). Now, the first successful preparation of a series of isolated ligand-free tetrameric Ca
Mn
O
(n=0-4) cluster ions is reported, which are employed as structural models for the catalytically active site of PS II. Gas-phase reactivity experiments with D
O and H
O in an ion trap reveal the facile deprotonation of multiple water molecules via hydroxylation of the cluster oxo bridges for all investigated clusters. However, only the mono-calcium cluster CaMn
O
is observed to oxidize water via elimination of hydrogen peroxide. First-principles density functional theory (DFT) calculations elucidate mechanistic details of the deprotonation and oxidation reactions mediated by CaMn
O
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O
⋅MnO cluster located in photosystem II (PS II). Now, the first successful preparation of a series of isolated ligand-free tetrameric Ca
Mn
O
(n=0-4) cluster ions is reported, which are employed as structural models for the catalytically active site of PS II. Gas-phase reactivity experiments with D
O and H
O in an ion trap reveal the facile deprotonation of multiple water molecules via hydroxylation of the cluster oxo bridges for all investigated clusters. However, only the mono-calcium cluster CaMn
O
is observed to oxidize water via elimination of hydrogen peroxide. First-principles density functional theory (DFT) calculations elucidate mechanistic details of the deprotonation and oxidation reactions mediated by CaMn
O
as well as the role of calcium.</abstract><cop>Germany</cop><pmid>30985054</pmid><doi>10.1002/anie.201903738</doi><tpages>6</tpages><orcidid>https://orcid.org/0000-0001-7851-0850</orcidid><orcidid>https://orcid.org/0000-0002-1586-1554</orcidid></addata></record> |
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| title | A Gas-Phase Ca n Mn 4-n O 4 + Cluster Model for the Oxygen-Evolving Complex of Photosystem II |
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