Kanady, Jacob S. and Lin, Po-Heng and Carsch, Kurtis M. and Nielsen, Robert J. and Takase, Michael K. and Goddard, William A., III and Agapie, Theodor (2014) Toward Models for the Full Oxygen-Evolving Complex of Photosystem II by Ligand Coordination To Lower the Symmetry of the Mn_3CaO_4 Cubane: Demonstration That Electronic Effects Facilitate Binding of a Fifth Metal. Journal of the American Chemical Society, 136 (41). pp. 14373-14376. ISSN 0002-7863. PMCID PMC4210109. https://resolver.caltech.edu/CaltechAUTHORS:20141008-093243995
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Abstract
Synthetic model compounds have been targeted to benchmark and better understand the electronic structure, geometry, spectroscopy, and reactivity of the oxygen-evolving complex (OEC) of photosystem II, a low-symmetry Mn_4CaO_n cluster. Herein, low-symmetry Mn^(IV)_3GdO_4 and Mn^(IV_)3CaO_4 cubanes are synthesized in a rational, stepwise fashion through desymmetrization by ligand substitution, causing significant cubane distortions. As a result of increased electron richness and desymmetrization, a specific μ_3-oxo moiety of the Mn_3CaO_4 unit becomes more basic allowing for selective protonation. Coordination of a fifth metal ion, Ag+, to the same site gives a Mn_3CaAgO_4 cluster that models the topology of the OEC by displaying both a cubane motif and a “dangler” transition metal. The present synthetic strategy provides a rational roadmap for accessing more accurate models of the biological catalyst.
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Alternate Title: | Toward Models for the Full Oxygen-Evolving Complex of Photosystem II by Ligand Coordination To Lower the Symmetry of the Mn3CaO4 Cubane: Demonstration That Electronic Effects Facilitate Binding of a Fifth Metal | |||||||||||||||
Additional Information: | © 2014 American Chemical Society. ACS AuthorChoice - This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes. Received: August 8, 2014. Publication Date (Web): September 20, 2014. This work was supported by the California Institute of Technology, the NIH (R01 GM102687A, T.A.), the NSF GRFP (J.S.K.), and NSF (CHE-1214158, W.A.G.). T.A. is a Sloan, Dreyfus, and Cottrell fellow. We thank Lawrence M. Henling for assistance with crystallography. The Bruker KAPPA APEXII X-ray diffractometer was purchased via an NSF Chemistry Research Instrumentation award to Caltech (CHE-0639094). | |||||||||||||||
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Issue or Number: | 41 | |||||||||||||||
PubMed Central ID: | PMC4210109 | |||||||||||||||
Record Number: | CaltechAUTHORS:20141008-093243995 | |||||||||||||||
Persistent URL: | https://resolver.caltech.edu/CaltechAUTHORS:20141008-093243995 | |||||||||||||||
Official Citation: | Toward Models for the Full Oxygen-Evolving Complex of Photosystem II by Ligand Coordination To Lower the Symmetry of the Mn3CaO4 Cubane: Demonstration That Electronic Effects Facilitate Binding of a Fifth Metal Jacob S. Kanady, Po-Heng Lin, Kurtis M. Carsch, Robert J. Nielsen, Michael K. Takase, William A. Goddard, III, and Theodor Agapie Journal of the American Chemical Society 2014 136 (41), 14373-14376 | |||||||||||||||
Usage Policy: | No commercial reproduction, distribution, display or performance rights in this work are provided. | |||||||||||||||
ID Code: | 50258 | |||||||||||||||
Collection: | CaltechAUTHORS | |||||||||||||||
Deposited By: | Tony Diaz | |||||||||||||||
Deposited On: | 09 Oct 2014 21:36 | |||||||||||||||
Last Modified: | 09 Mar 2020 13:19 |
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