Resolving the manganese oxidation states in the oxygen-evolving catalyst of natural photosynthesis

Vera Krewald, Frank Neese, Dimitrios A. Pantazis

Research output: Contribution to journalReview articlepeer-review

25 Citations (SciVal)


A frequent challenge when dealing with multinuclear transition metal clusters in biology is to determine the absolute oxidation states of the individual metal ions and to identify how they evolve during catalytic turnover. The oxygen-evolving complex of biological photosynthesis, an active site that harbors an oxo-bridged Mn4Ca cluster as the water-oxidizing species, offers a prime example of such a challenge that withstood satisfactory resolution for decades. A multitude of experimental studies have approached this question and have offered insights from different angles, but they were also accompanied by incomplete or inconclusive interpretations. Only very recently, through a combination of experiment and theory, has a definitive assignment of the individual Mn oxidation states been achieved for all observable catalytic states of the complex. Here we review the information obtained by structural and spectroscopic methods, describe the interpretation and synthesis achieved through quantum chemistry, and summarize our current understanding of the electronic structure of nature's water splitting catalyst.

Original languageEnglish
Pages (from-to)1219-1232
Number of pages14
JournalIsrael Journal of Chemistry
Issue number11-12
Publication statusPublished - 1 Nov 2015


  • manganese
  • oxygen-evolving complex
  • photosynthesis
  • water splitting


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