論文

査読有り
2014年9月

Mechanism of water oxidation by non-heme iron catalysts when driven with sodium periodate

DALTON TRANSACTIONS
  • Alexander R. Parent
  • ,
  • Takashi Nakazono
  • ,
  • Shu Lin
  • ,
  • Satoshi Utsunomiya
  • ,
  • Ken Sakai

43
33
開始ページ
12501
終了ページ
12513
記述言語
英語
掲載種別
研究論文(学術雑誌)
DOI
10.1039/c4dt01188k
出版者・発行元
ROYAL SOC CHEMISTRY

Iron tris(2-methylpyridyl)amine (TPA) and iron 1-(bis(2-methylpyridyl)amino)-2-methyl-2-propanoate (BPyA) salts are characterized as water oxidation catalysts (WOCs) using sodium periodate. Under the conditions used, these complexes serve as homogeneous WOCs as demonstrated via kinetic analysis and dynamic light scattering (DLS). The Fe(BPyA) salt serves as both a mononuclear and dinuclear catalyst, with the mononuclear form showing higher catalytic activity. Based on the H/D kinetic isotope effect and pH dependence, the rate determining step (RDS) in water oxidation (WO) by Fe(BPyA) is nucleophilic attack by water during O-O bond formation. In contrast, Fe(TPA) shows complex kinetic behavior due to the formation of multiple oxidation states of the complex in solution, each of which exhibits catalytic activity for WO. The RDS in WO by Fe(TPA) follows an equilibrium established between monomeric and dimeric forms of the catalyst. Under acidic conditions formation of the monomer is favored, which leads to an increase in the WO rate.

Web of Science ® 被引用回数 : 44

リンク情報
DOI
https://doi.org/10.1039/c4dt01188k
Web of Science
https://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcAuth=JSTA_CEL&SrcApp=J_Gate_JST&DestLinkType=FullRecord&KeyUT=WOS:000340353100009&DestApp=WOS_CPL
ID情報
  • DOI : 10.1039/c4dt01188k
  • ISSN : 1477-9226
  • eISSN : 1477-9234
  • Web of Science ID : WOS:000340353100009

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