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Cited by 204Metal-Catalyzed Oxygenation MechanismsPhotosynthetic Processes and MechanismsMetalloenzymes and iron-sulfur proteins

Why did Nature choose manganese to make oxygen?

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Armstrong, Fraser A·2008·Philosophical Transactions of the Royal Society B: Biological Sciences
DOI 10.1098/rstb.2007.2223PMC PMC2614089
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Abstract

This paper discusses the suitability of manganese for its function in catalysing the formation of molecular oxygen from water. Manganese is an abundant element. In terms of its inherent properties, Mn has a particularly rich redox chemistry compared with other d-block elements, with several oxidizing states accessible. The most stable-state Mn 2+ behaves like a Group 2 element—it is mobile, weakly complexing, easily taken up by cells and redox-inactive in simple aqueous media. Only in the presence of suitable ligands does Mn 2+ become oxidized, so it provides an uncomplicated building unit for the oxygen-evolving centre (OEC). The intermediate oxidation states Mn(III) and Mn(IV) are strongly complexed by O 2− and form robust mixed-valence poly-oxo clusters in which the Mn(IV)/Mn(III) ratio can be elevated, one electron at a time, accumulating oxidizing potential and capacity. The OEC is a Mn 4 CaO x cluster that undergoes sequential oxidations by P680 + at potentials above 1 V, ultimately to a super-oxidized level that includes one Mn(V) or a Mn(IV)-oxyl radical. The latter is powerfully oxidizing and provides the crucial ‘power stroke’ necessary to generate an O–O bond. This leaves a centre still rich in Mn(IV), ensuring a rapid follow-through to O 2 .

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  • Manganese is essential for the oxygen-evolving complex of photosystem II, the defining feature of oxygenic photosynthesis.

    “Of note, manganese is essential for the oxygen-evolving complex of photosystem II that is the defining feature of oxygenic photosynthesis.98”

    From Metals in Motion: Understanding Labile Metal Pools in Bacteria (2025) · cites this paper as [98]

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Authors
Armstrong, F. A.
Affiliations
University of Oxford (GB)
Corresponding author
Armstrong, Fraser A
ORCID
Armstrong, Fraser A
Venue
Philosophical Transactions of the Royal Society B: Biological Sciences
Publisher
The Royal Society
Published
2007-10-30
Volume
363
Issue
1494
Pages
1263-1270
ISSN
  • 0962-8436 (ISSN-L)
  • 1471-2970
DOI
10.1098/rstb.2007.2223
PMC
PMC2614089
OpenAlex
W2121526477
Cited by
204
References
0
Citations by year
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FWCI
0.35
Type
journal article
Language
en
Open access
Licence
royalsociety.org/journals/ethics-policies/data-sharing-mining/ (tdm)
Locations
  • Philosophical Transactions of the Royal Society B Biological Sciences (publishedVersion)
  • PubMed Central (publishedVersion)
  • PubMed (publishedVersion)
Funders
Biotechnology and Biological Sciences Research Council
Topics
  • Physical Sciences › Chemistry › Inorganic Chemistry › Metal-Catalyzed Oxygenation Mechanisms
  • Life Sciences › Biochemistry, Genetics and Molecular Biology › Molecular Biology › Photosynthetic Processes and Mechanisms
  • Physical Sciences › Energy › Renewable Energy, Sustainability and the Environment › Metalloenzymes and iron-sulfur proteins
Keywords
manganese, photosynthesis, water oxidation, redox chemistry, P680, manganese oxidation state, catalytic mechanism
MeSH terms
Catalysis, Manganese, Models, Chemical, Oxidation-Reduction, Oxygen, Water, Photosystem II Protein Complex

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