High-spin Mn–oxo complexes and their relevance to the oxygen-evolving complex within photosystem II
Abstract
The structural and electronic properties of a series of manganese complexes with terminal oxido ligands are described. The complexes span three different oxidation states at the manganese center (III–V), have similar molecular structures, and contain intramolecular hydrogen-bonding networks surrounding the Mn–oxo unit. Structural studies using X-ray absorption methods indicated that each complex is mononuclear and that oxidation occurs at the manganese centers, which is also supported by electron paramagnetic resonance (EPR) studies. This gives a high-spin Mn V –oxo complex and not a Mn IV –oxy radical as the most oxidized species. In addition, the EPR findings demonstrated that the Fermi contact term could experimentally substantiate the oxidation states at the manganese centers and the covalency in the metal–ligand bonding. Oxygen-17–labeled samples were used to determine spin density within the Mn–oxo unit, with the greatest delocalization occurring within the Mn V –oxo species (0.45 spins on the oxido ligand). The experimental results coupled with density functional theory studies show a large amount of covalency within the Mn–oxo bonds. Finally, these results are examined within the context of possible mechanisms associated with photosynthetic water oxidation; specifically, the possible identity of the proposed high valent Mn–oxo species that is postulated to formmore »
- Authors:
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); National Institutes of Health (NIH); National Science Foundation (NSF)
- OSTI Identifier:
- 1235170
- Alternate Identifier(s):
- OSTI ID: 1512187
- Grant/Contract Number:
- AC02-05CH11231
- Resource Type:
- Published Article
- Journal Name:
- Proceedings of the National Academy of Sciences of the United States of America
- Additional Journal Information:
- Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Volume: 112 Journal Issue: 17; Journal ID: ISSN 0027-8424
- Publisher:
- Proceedings of the National Academy of Sciences
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; metal–oxo complexes; water oxidation; inorganic chemistry; photosynthesis; oxygen-evolving complex
Citation Formats
Gupta, Rupal, Taguchi, Taketo, Lassalle-Kaiser, Benedikt, Bominaar, Emile L., Yano, Junko, Hendrich, Michael P., and Borovik, A. S. High-spin Mn–oxo complexes and their relevance to the oxygen-evolving complex within photosystem II. United States: N. p., 2015.
Web. doi:10.1073/pnas.1422800112.
Gupta, Rupal, Taguchi, Taketo, Lassalle-Kaiser, Benedikt, Bominaar, Emile L., Yano, Junko, Hendrich, Michael P., & Borovik, A. S. High-spin Mn–oxo complexes and their relevance to the oxygen-evolving complex within photosystem II. United States. doi:10.1073/pnas.1422800112.
Gupta, Rupal, Taguchi, Taketo, Lassalle-Kaiser, Benedikt, Bominaar, Emile L., Yano, Junko, Hendrich, Michael P., and Borovik, A. S. Tue .
"High-spin Mn–oxo complexes and their relevance to the oxygen-evolving complex within photosystem II". United States. doi:10.1073/pnas.1422800112.
@article{osti_1235170,
title = {High-spin Mn–oxo complexes and their relevance to the oxygen-evolving complex within photosystem II},
author = {Gupta, Rupal and Taguchi, Taketo and Lassalle-Kaiser, Benedikt and Bominaar, Emile L. and Yano, Junko and Hendrich, Michael P. and Borovik, A. S.},
abstractNote = {The structural and electronic properties of a series of manganese complexes with terminal oxido ligands are described. The complexes span three different oxidation states at the manganese center (III–V), have similar molecular structures, and contain intramolecular hydrogen-bonding networks surrounding the Mn–oxo unit. Structural studies using X-ray absorption methods indicated that each complex is mononuclear and that oxidation occurs at the manganese centers, which is also supported by electron paramagnetic resonance (EPR) studies. This gives a high-spin Mn V –oxo complex and not a Mn IV –oxy radical as the most oxidized species. In addition, the EPR findings demonstrated that the Fermi contact term could experimentally substantiate the oxidation states at the manganese centers and the covalency in the metal–ligand bonding. Oxygen-17–labeled samples were used to determine spin density within the Mn–oxo unit, with the greatest delocalization occurring within the Mn V –oxo species (0.45 spins on the oxido ligand). The experimental results coupled with density functional theory studies show a large amount of covalency within the Mn–oxo bonds. Finally, these results are examined within the context of possible mechanisms associated with photosynthetic water oxidation; specifically, the possible identity of the proposed high valent Mn–oxo species that is postulated to form during turnover is discussed.},
doi = {10.1073/pnas.1422800112},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 17,
volume = 112,
place = {United States},
year = {2015},
month = {4}
}
DOI: 10.1073/pnas.1422800112
Web of Science
Figures / Tables:

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