Absence of Mn-centered oxidation in the S2 → S3 Transition:: Implications for the mechanism of photosynthetic water oxidation

Absence of Mn-centered oxidation in the S2 → S3 Transition: : Implications for the mechanism of photosynthetic water oxidation

Robblee, J H (author)

Bergmann, U (author)

Fernandez, C (author)

Glatzel, P (author)

Visser, H (author)

Cinco, R M (author)

McFarlane, K L (author)

Bellacchio, E (author)

Pizarro, S A (author)

Cramer, S P (author)

Sauer, K (author)

Klein, M P (author)

Yachandra, V K (author)

(creator_code:org_t)

2001-07-20
2001
English.
In: Journal of the American Chemical Society. - : AMER CHEMICAL SOC. - 0002-7863 .- 1520-5126. ; 123:32, s. 7804-7820

Related links:: https://europepmc.or...; show more...; https://urn.kb.se/re...; https://doi.org/10.1...; show less...

Abstract Subject headings

A key question for the understanding of photosynthetic water oxidation is whether the four oxidizing equivalents necessary to oxidize water to dioxygen are accumulated on the four Mn ions of the oxygen-evolving complex (OEC), or whether some ligand-centered oxidations take place before the formation and release of dioxygen during the S-3 --> [S-4] --> So transition. Progress in instrumentation and flash sample preparation allowed us to apply Mn K beta X-ray emission spectroscopy (K beta XES) to this problem for the first time. The K beta XES results, in combination with Mn X-ray absorption near-edge structure (XANES) and electron paramagnetic resonance (EPR) data obtained from the same set of samples, show that the S-2 --> S3 transition, in contrast to the S-0 --> S-1 and S-1 --> S-2 transitions. does not involve a Mn-centered oxidation. On the basis of new structural data from the S-3-state, manganese mu -oxo bridge radical formation is proposed for the S-2 --> S-3 transition, and three possible mechanisms for the O-O bond formation are presented.

By the author/editor: Messinger, Johan ...; Robblee, J H; Bergmann, U; Fernandez, C; Glatzel, P; Visser, H; show more...; Cinco, R M; McFarlane, K L; Bellacchio, E; Pizarro, S A; Cramer, S P; Sauer, K; Klein, M P; Yachandra, V K; show less...

About the subject

NATURAL SCIENCES: NATURAL SCIENCES; and Biological Scien ...; and Biochemistry and ...

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