論文

査読有り
2018年11月

Electron and Hydride Transfer in a Redox-Active NiFe Hydride Complex: A DFT Study

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

8
11
開始ページ
10419
終了ページ
10429
記述言語
英語
掲載種別
研究論文(学術雑誌)
DOI
10.1021/acscatal.8b02368
出版者・発行元
AMER CHEMICAL SOC

We present mechanistic details of the formation of a NiFe hydride complex and provide information on its electron-and hydride-transfer processes on the basis of density functional theory calculations and artificial-force induced-reaction studies. The NiFe hydride complex conducts three transfer reactions: namely, electron transfer, hydride transfer, and proton transfer. In a NiFe hydride complex, the hydride binds to Fe, which is different from the Ni-R state in hydrogenase where the hydride is located between Ni and Fe. According to our calculations, in reaction with the ferrocenium ion, electron transfer occurs from the NiFe hydride complex to the ferrocenium ion, followed by a hydrogen atom transfer (HAT) to the second ferrocenium ion. The oxidation state of Fe varies during the redox process, different from the case of NiFe hydrogenase, where the oxidation state of Ni varies. A single-step hydride transfer occurs in the presence of a 10-methylacridinium ion (AcrH(+)), which is more kinetically feasible than the HAT process. In contrast to the HAT and hydride-transfer process, the proton transfer occurs through a low barrier from a protonated diethyl ether. The revealed reaction mechanism guides the interpretation of the catalytic cycle of NiFe hydrogenase and leads to the development of efficient biomimetic catalysts for H-2 generation and an electron/hydride transfer.

Web of Science ® 被引用回数 : 6

リンク情報
DOI
https://doi.org/10.1021/acscatal.8b02368
Web of Science
https://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcAuth=JSTA_CEL&SrcApp=J_Gate_JST&DestLinkType=FullRecord&KeyUT=WOS:000449723900056&DestApp=WOS_CPL

エクスポート
BibTeX RIS