title: Structural and spectroscopic investigation of an anilinosalen cobalt complex with relevance to hydrogen production.
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.
authors.affiliation: Max Planck Institute for Chemical Energy Conversion , Stiftstrasse 34-36, D-45470 Mülheim an der Ruhr, Germany.
authors.forename: Amélie
authors.initials: A
authors.lastname: Kochem
authors.forename: Fabrice
authors.initials: F
authors.lastname: Thomas
authors.forename: Olivier
authors.initials: O
authors.lastname: Jarjayes
authors.forename: Gisèle
authors.initials: G
authors.lastname: Gellon
authors.forename: Christian
authors.initials: C
authors.lastname: Philouze
authors.forename: Thomas
authors.initials: T
authors.lastname: Weyhermüller
authors.forename: Frank
authors.initials: F
authors.lastname: Neese
authors.forename: Maurice
authors.initials: M
authors.lastname: van Gastel