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Resolving the Manganese Oxidation States in the Oxygen‐evolving Catalyst of Natural Photosynthesis
Author(s) -
Krewald Vera,
Neese Frank,
Pantazis Dimitrios A.
Publication year - 2015
Publication title -
israel journal of chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.908
H-Index - 54
eISSN - 1869-5868
pISSN - 0021-2148
DOI - 10.1002/ijch.201500051
Subject(s) - chemistry , oxidizing agent , catalysis , manganese , chemical physics , photosynthesis , oxygen , oxygen evolution , cluster (spacecraft) , artificial photosynthesis , observable , transition metal , oxygen evolving complex , metal , nanotechnology , computational chemistry , photosystem ii , organic chemistry , electrochemistry , physics , quantum mechanics , computer science , programming language , biochemistry , materials science , electrode , photocatalysis
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 Mn 4 Ca 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.