Electron Transfer and Geometric Conversion of Co-NO Moiety in Saddled Porphyrins: Implications for Trigger Role of Tetrapyrrole Distortion

Min Tang, Yan Yang, Shaowei Zhang, Jiafu Chen, Jian Zhang, Zaichun Zhou, Qiuhua Liu

Research output: Contribution to journalArticle

6 Scopus citations

Abstract

The electrons of NO and Co are strongly delocalized in normal {Co-NO}8 species. In this work, {Co-NO}8 complexes are induced to convert from (CoII)+•-NO to CoIII-NO- by a core contraction of 0.06 Å in saddled cobalt(II) porphyrins. This intramolecular electron transfer mechanism indicates that nonplanarity of porphyrin is involved in driving conversion of the NO units from electrophilic NO as a bent geometry to nucleophilic NO- as a linear geometry. This implies that distortion acts as a trigger in enzymes containing tetrapyrrole. The electronic behaviors of the CoII ions and Co-NO moieties were confirmed by X-ray crystallography, EPR spectroscopy, theoretical calculation, UV-vis and IR spectroscopy, and electrochemistry.

Original languageEnglish (US)
Pages (from-to)277-287
Number of pages11
JournalInorganic Chemistry
Volume57
Issue number1
DOIs
StatePublished - Jan 2 2018

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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