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Structural and Spectroscopic Investigation of an Anilinosalen Cobalt Complex with Relevance to Hydrogen Production

MPS-Authors
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Kochem,  Amélie
Research Department Neese, Max Planck Institute for Chemical Energy Conversion, Max Planck Society;

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Weyhermüller,  Thomas
Research Department Neese, Max Planck Institute for Chemical Energy Conversion, Max Planck Society;

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Neese,  Frank
Research Department Neese, Max Planck Institute for Chemical Energy Conversion, Max Planck Society;

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van Gastel,  Maurice
Research Department Neese, Max Planck Institute for Chemical Energy Conversion, Max Planck Society;

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Citation

Kochem, A., Thomas, F., Jarjayes, O., Gellon, G., Philouze, C., Weyhermüller, T., et al. (2013). Structural and Spectroscopic Investigation of an Anilinosalen Cobalt Complex with Relevance to Hydrogen Production. Inorganic Chemistry, 52(24), 14428-14438. doi:10.1021/ic402818g.


Cite as: https://hdl.handle.net/21.11116/0000-0007-CE32-9
Abstract
A Co(II) anilinosalen catalyst containing proton relays in the first coordination sphere has been synthesized that catalyzes the electrochemical production of hydrogen from acid in dichloromethane and acetonitrile solutions. The complex has been spectroscopically and theoretically characterized in different protonation and redox states. We show that both coordinated anilido groups of the neutral Co(II) complex can be protonated into aniline form. Protonation induces an anodic shift of more than 1 V of the reduction wave, which concomitantly becomes irreversible. Hydrogen evolution that originates from the aniline protons located in the first coordination sphere is observed upon bulk electrolysis at −1.5 V of the protonated complex in absence of external acid. Structures for intermediates in the catalytic reaction have been identified based on this data.