論文

査読有り
2018年5月

DFT Study on Fe(IV)-Peroxo Formation and H Atom Transfer Triggered O-2 Activation by NiFe Complex

ORGANOMETALLICS
  • Miho Isegawa
  • ,
  • Akhilesh K. Sharma
  • ,
  • Seiji Ogo
  • ,
  • Keiji Morokuma

37
10
開始ページ
1534
終了ページ
1545
記述言語
英語
掲載種別
研究論文(学術雑誌)
DOI
10.1021/acs.organomet.8b00098
出版者・発行元
AMER CHEMICAL SOC

The mechanism for dioxygen activation using the biomimetic model complex of [NiFe]-hydrogenase, [NiLFe(eta(5)-C5Me5 )](+) [L = N,N'-diethyl-3,7-diazanonane-1,9-dithiolato] was established using density functional theory (DFT) and artificial force-induced reaction (AFIR) methods. Our computational results suggest that O-2 binds to the Fe-II center in an end-on fashion and forms a high-valent iron complex, ((NiFeIV)-Fe-II(eta(2)-O-2) NiFe-peroxo O-2)), which has been experimentally observed. The O-O bond cleavage occurs in the presence of borohydride (BH4-) through hydrogen atom transfer (HAT). Once the HAT occurs, the generated BH 3 radical anion (BH3 center dot-) binds to the terminal oxygen of NiFe-OOH, giving rise to BH3OH- and (NiFeIV)-Fe-II=O. The second HAT from BH4- to the oxygen of (NiFeIV)-Fe-II=O leads to BH3OH- and Fe-reduced complex. Importantly, the dioxygen activation is triggered by HAT, not by proton transfer or hydride transfer. The O-2 is activated by the Fe center, and the oxidation state of Fe varies during the process, while the oxidation state of Ni is conserved. These mechanistic insights into O-2 activation are essential in understanding the formation of the inactive state and reactivation process in hydrogenase.

Web of Science ® 被引用回数 : 6

リンク情報
DOI
https://doi.org/10.1021/acs.organomet.8b00098
Web of Science
https://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcAuth=JSTA_CEL&SrcApp=J_Gate_JST&DestLinkType=FullRecord&KeyUT=WOS:000433635600004&DestApp=WOS_CPL

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