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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

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.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/ja508160xDOIArticle
http://pubs.acs.org/doi/abs/10.1021/ja508160xPublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/ja508160xPublisherSupporting Information
https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4210109/PubMed CentralArticle
ORCID:
AuthorORCID
Carsch, Kurtis M.0000-0003-4432-7518
Nielsen, Robert J.0000-0002-7962-0186
Takase, Michael K.0000-0001-8365-3645
Goddard, William A., III0000-0003-0097-5716
Agapie, Theodor0000-0002-9692-7614
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).
Funders:
Funding AgencyGrant Number
CaltechUNSPECIFIED
NIHR01 GM102687A
NSF Graduate Research FellowshipUNSPECIFIED
NSFCHE-1214158
NSFCHE-0639094
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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