DOI: 10.1002/anie.200502114. Water Oxidation Catalyzed by a Dinuclear Mn Complex: A Functional Model for the Oxygen‐Evolving Center of Photosystem II

Water Oxidation Catalyzed by a Dinuclear Mn Complex: A Functional Model for the Oxygen‐Evolving Center of Photosystem II

10.1002/anie.200502114

Crossref journal-article

Wiley

Angewandte Chemie International Edition (311)

Bibliography

Poulsen, A. K., Rompel, A., & McKenzie, C. J. (2005). Water Oxidation Catalyzed by a Dinuclear Mn Complex: A Functional Model for the OxygenâEvolving Center of Photosystem II. Angewandte Chemie International Edition, 44(42), 6916â6920. Portico.

Authors 3

Allan K. Poulsen (first)
Annette Rompel (additional)
Christine J. McKenzie (additional)

References 29 Referenced 204

10.1021/cr0206014
10.1039/b300823a
10.1002/(SICI)1098-2787(2000)19:1<1::AID-MAS1>3.0.CO;2-Y
10.1021/ac950998u
10.1111/j.1574-6968.2004.tb09656.x
MIMS is a method that allows the analysis of volatile compounds in liquid media. The only separation between the polar media and the mass spectrometer is a thin polymer film. Volatile and hydrophobic compounds dissolve in the membrane diffuse through it and evaporate into the ion source of the mass spectrometer where they are ionized and analyzed according to their mass‐to‐charge ratios. The method is highly suited for measuring gases and organic compounds in aqueous media and enables measurements in the low‐ppm range. The response time is only a few seconds and the method has been used for studies of complex chemical reactions[26]and for online measurements in microbial media.[5]We have attempted to assess the electron‐impact mass spectrometry (EIMS) methods used in the analysis of18O‐labelling experiments in references [20 23 24]. Unfortunately insufficient detail was provided (in supplementary information) to describe the experimental protocols. Thus we assume that the gas in the head space over the reactions was analyzed. This method is fundamentally different to MIMS and is not quantitative.
A deliberate injection of O2into the system does not invoke this response rather the surge is recorded and this immediately decays exponentially.
We are currently designing a new cell so that a continuous supply of TBHP can be added in order to attain a steady state of catalytic activity. Visual inspection of the reactions indicates that the concentrations used in the MIMS experiments are not optimal and the system potentially produces much greater amounts of product.
We have not found determinations of O‐exchange between water andtBuOOH in the literature. However the specific production of one isotopomer observed in our work is indirect evidence that any exchange of this nature is not kinetically relevant. If there was significant exchange then a distribution of isotopes 16O2 18O16O and18O2 would be observed. Furthermore we have monitored the reaction solution atm/z92 which corresponds to singly18O‐labeled TBHP. No trace was detected (and we do see unlabeled TBHP atm/z90). Therefore competing homolytic cleavage of the OO bond in TBHP and consequent radical Haber–Weiss chemistry can be eliminated in mechanistic considerations. Furthermore oxidation is observed with the CeIVoxidant.
The complex is dimeric in solution as well as in the solid state as evidenced by solution ESR spectroscopy.[2]
bispicen=N N′‐bis(2‐methylpyridyl)ethane‐1 2‐diamine.
10.1039/C39870001659
10.1021/ic00096a040
10.1021/ic00328a034
10.1126/science.271.5254.1397
10.1002/1521-3757(20020402)114:7<1160::AID-ANGE1160>3.0.CO;2-0
10.1002/1521-3773(20020402)41:7<1114::AID-ANIE1114>3.0.CO;2-6
10.1002/1521-3757(20020603)114:11<1900::AID-ANGE1900>3.0.CO;2-E
10.1002/1521-3773(20020603)41:11<1821::AID-ANIE1821>3.0.CO;2-4
The reaction is not a catalase‐like reaction. If this were the case both O atoms would be derived from the oxidant.
10.1021/ja00378a053
10.1021/ja00299a017
10.1021/ja039780c
The nitrate complex (NH4)2[Ce(NO3)6] is that normally used as a source of CeIVin oxidation reactions. However participation by the nitrate ion is not normally considered.
As mentioned in the text the nitrate‐containing [MnIII(mcbpen)NO3]+is in fact observed in the ESI mass spectra of the reaction solutions. This fact cannot be regarded as evidence for Mn activation for nitrate reduction. However it does suggest a higher concentration of [MnIII(mcbpen)NO3]+than the isoelectronic [MnIII(mcbpen)OH]+ which is seen in the TBHP reactions. An attempt to verify the possible involvement of nitrate in the water oxidation was made by adding a 100‐fold excess of sodium nitrate to the reaction. This resulted in complete inhibition of the reaction. This observation is not surprising if nitrate is capable of substituting the water ligands of1‐2 (ClO4)2and consequently inhibiting the reaction. We have also attempted to detect the N18O16O2−isotopomer by negative‐ion ESIMS. Unfortunately in the presence of such large excess of the unlabeled nitrate this experiment was beyond the resolution capabilities of our instrument.
10.1126/science.283.5407.1524
10.1021/ja001090a
10.1126/science.1093087
10.1021/j100344a017

Dates

Type	When
Created	19 years, 10 months ago (Oct. 5, 2005, 4:49 a.m.)
Deposited	1 year, 10 months ago (Oct. 10, 2023, 12:55 p.m.)
Indexed	2 weeks, 4 days ago (Aug. 12, 2025, 5:31 p.m.)
Issued	19 years, 10 months ago (Oct. 25, 2005)
Published	19 years, 10 months ago (Oct. 25, 2005)
Published Online	19 years, 10 months ago (Oct. 25, 2005)
Published Print	19 years, 10 months ago (Oct. 28, 2005)

Funders 0

None

BibTeX

@article{Poulsen_2005, title={Water Oxidation Catalyzed by a Dinuclear Mn Complex: A Functional Model for the Oxygen‐Evolving Center of Photosystem II}, volume={44}, ISSN={1521-3773}, url={http://dx.doi.org/10.1002/anie.200502114}, DOI={10.1002/anie.200502114}, number={42}, journal={Angewandte Chemie International Edition}, publisher={Wiley}, author={Poulsen, Allan K. and Rompel, Annette and McKenzie, Christine J.}, year={2005}, month=oct, pages={6916–6920} }

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