Mechanism for photosynthetic O2 evolution

Proc Natl Acad Sci U S A. 1986 Jul;83(13):4586-8. doi: 10.1073/pnas.83.13.4586.

Abstract

We present a mechanism for photosynthetic O2 evolution based on a structural conversion of a Mn4O6 "adamantane"-like complex to a Mn4O4 "cubane"-like complex. EPR spectral data obtained from the S2 state of the O2-evolving complex are characteristic of a Mn4O4 cubane-like structure. Based on this structure for the manganese complex in the S2 state as well as a consideration of the other evidence available on the natural system and the coordination chemistry of manganese, structures are proposed for the five intermediate oxidation states of the manganese complex. A molecular mechanism for the formation of an O--O bond and the displacement of O2 from the S4 state is easily accommodated by the proposed model. The model is discussed in terms of recent EPR, x-ray, and UV spectral data obtained from the manganese site in the photosynthetic O2-evolving complex.

Publication types

  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, P.H.S.

MeSH terms

  • Manganese*
  • Models, Chemical
  • Oxidation-Reduction
  • Oxygen*
  • Photosynthesis*

Substances

  • Manganese
  • Oxygen