Theory of chemical bonds in metalloenzymes VI: Manganese-oxo bonds in the photosynthesis II system

K. Yamaguchi, S. Yamanaka, H. Isobe, M. Shoji, K. Koizumi, Y. Kitagawa, T. Kawakami, M. Okumura

Research output: Contribution to journalArticlepeer-review

47 Citations (Scopus)


Electronic and spin structures of high-valent manganese-oxo bonds in the photosynthesis II system (oxygen evolving center, OEC) are investigated by the use of spin polarized hybrid DFT (HDFT) method. Theoretical calculations of a high-valent manganese-oxo porphyrin complex are also performed to elucidate common characteristic of the active Mn{double bond, long}O bonds in both native OEC and artificial systems. The oxygen site of the high-valent Mn{double bond, long}O is found to be electrophilic in nature, in accord with our previous work, where the SE2, 1O- and 3O-models have been presented for theoretical understanding of complex behaviors of oxygenation reactions by metal-oxo species. The 1O- and 3O-models are applicable to model complexes examined here, since the manganese-oxo bonds exhibit strong biradical character. Possibility of the SE2-like transition structure model for OEC is also discussed on both the theoretical and experimental grounds. Implications of present computational results are discussed in relation to hydroxylation reaction by MMO and P450.

Original languageEnglish
Pages (from-to)2216-2224
Number of pages9
Issue number9-11
Publication statusPublished - Jun 15 2007
Externally publishedYes


  • B3LYP
  • Manganese-oxo bond
  • Oxygen evolution
  • Photosynthesis II
  • SE reaction

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry


Dive into the research topics of 'Theory of chemical bonds in metalloenzymes VI: Manganese-oxo bonds in the photosynthesis II system'. Together they form a unique fingerprint.

Cite this