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

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

    Research output: Contribution to journalArticlepeer-review

    15 Citations (Scopus)


    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 H2 generation and an electron/hydride transfer.

    Original languageEnglish
    Pages (from-to)10419-10429
    Number of pages11
    JournalACS Catalysis
    Issue number11
    Publication statusPublished - Nov 2 2018

    All Science Journal Classification (ASJC) codes

    • Catalysis
    • General Chemistry


    Dive into the research topics of 'Electron and Hydride Transfer in a Redox-Active NiFe Hydride Complex: A DFT Study'. Together they form a unique fingerprint.

    Cite this