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Cobaloxime-Based Double Complex Salts as Efficient and Versatile Catalysts for the Light-Driven Hydrogen Evolution Reaction

submitted on 07.01.2020, 16:45 and posted on 08.01.2020, 21:16 by Elisabeth Hofmeister, Jisoo Woo, Tobias Ullrich, Lydia Petermann, Kevin Hanus, Sven Rau, Axel Kahnt, Max von Delius
Cobaloximes and their BF2-bridged analogues have emerged as promising non-noble metal catalysts for the photocatalytic hydrogen evolution reaction (HER). Herein we report the serendipitous discovery that double complex salts such as [Co(dmgh)2py2]+[Co(dmgBPh2)2Cl2]- can be obtained in good yields by treatment of commercially available [Co(dmgh)2pyCl] with triarylboranes. A systematic study on the use of such double complex salts and their single salts with simple counterions as photocatalysts revealed HER activities comparable or superior to existing cobaloxime catalysts and suggests ample opportunities for this compound class in catalyst/photosensitizer dyads and immobilized architectures. Preliminary electrochemical and spectroscopic studies indicate that one key advantage of these charged cobalt complexes is that the reduction potentials as well as the electrostatic interaction with charged photosensitizers can be tuned.


Deutsche Forschungsgemeinschaft (DFG – German Research Foundation) – project number 364549901 – TRR 234


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University of Ulm



ORCID For Submitting Author


Declaration of Conflict of Interest

no conflict of interest