Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 136, Issue 41, Pages 14373-14376Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ja508160x
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Funding
- California Institute of Technology
- NIH [R01 GM102687A]
- NSF GRFP
- NSF [CHE-1214158]
- NSF Chemistry Research Instrumentation award [CHE-0639094]
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [1214158] Funding Source: National Science Foundation
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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 Mn4CaOn cluster. Herein, low-symmetry (Mn3GdO4)-Gd-IV and (Mn3CaO4)-Ca-IV 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 mu(3)-oxo moiety of the Mn3CaO4 unit becomes more basic allowing for selective protonation. Coordination of a fifth metal ion, Ag+, to the same site gives a Mn3CaAgO4 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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