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![Protein Film Infrared Electrochemistry Demonstrated for Study of H2 Oxidation by a [NiFe] Hydrogenase](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F55858.jpg&w=3840&q=50)
Protein Film Infrared Electrochemistry Demonstrated for Study of H2 Oxidation by a [NiFe] Hydrogenase
Published on: December 4, 2017
Electrochemical behaviors of a pincer-type NNN-Fe complex and catalytic H2 evolution activity
Seungjin Song1, Junseong Lee2, Jun-Ho Choi1
1Department of Chemistry, Gwangju Institute of Science and Technology, Gwangju 61005, Republic of Korea. seojh@gist.ac.kr.
Abstract:
We describe electrochemical reactivity of a pincer-type [NNN-Fe(tBuNC)3](ClO4)2 complex. Upon electron reduction, the Fe(i) species experienced disproportionation to Fe(0) and Fe(ii). An electron-reduced Fe center dissociated a tBuNC ligand to make an open coordination site, where a proton could be transferred. The low-spin Fe center, assisted by isocyanide and a pyridine-based NNN-pincer ligand, catalyzed efficiently the proton reduction reaction. Also, a Lewis basic amine site in the side 'arm' of the NNN-pincer ligand lowered the free energy for the protonation of an Fe center during the proton reduction process. DFT calculations provided insight into a plausible catalytic pathway.
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