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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
Spin-reconstructed proton-coupled electron transfer in a ferrocene-nickeladithiolene hybrid
Akira Tanushi1, Tetsuro Kusamoto1, Yohei Hattori1
1Department of Chemistry, Graduate School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
Abstract:
A proton-electron dual-responsive system based on a hybrid of ferrocene and metalladithiolene (1) was developed. The formation of the dithiafulvenium moiety was driven by protonation of the metalladithiolene unit of 1 and by oxidation. The change in the electronic structure caused by the protonation was combined with the redox properties of the two components of 1, generating two radical species with different spin density distributions (3d spin and π spin). Furthermore, a spin-reconstructed proton-coupled electron transfer, i.e., the transformation from 3d spin to π spin accompanied by deprotonation, was achieved by a temperature change, the third external stimulus.
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