Cobalt-Catalyzed Hydrogenation Reactions Enabled by Ligand-Based Storage of Dihydrogen

27 May 2022, Version 1
This content is a preprint and has not undergone peer review at the time of posting.


The use of supporting ligands which can store either protons or electrons has emerged as a powerful strategy in catalysis. While these strategies are potent individually, natural systems mediate remarkable transformations by combining storage of both protons and electrons in the secondary coordination sphere. As such, there has been recent interest in using this strategy to enable fundamentally new transformations. Furthermore, outsourcing H-atom or hydrogen storage to ancillary ligands can also enable new mechanistic pathways and thereby selectivity. Here we describe the application of this strategy to facilitate radical reactivity in Co-based hydrogenation catalysis. Metalation of previously reported dihydrazonopyrrole ligands with Co results in paramagnetic complexes which are best described as having Co(II) oxidation states. These complexes catalytically hydrogenate olefins with low catalyst loadings under mild conditions (1 atm H2, 23 °C). Mechanistic, spectroscopic, and computational investigations indicate that this system goes through a radical hydrogen-atom transfer (HAT) type pathway that is distinct from classic organometallic mechanisms and is supported by the ability of the ligand to store H2. These results show how ancillary ligands can facilitate efficient catalysis and furthermore how classic organometallic mechanisms for catalysis can be altered by the secondary coordination sphere.


metal-ligand cooperativity

Supplementary materials

Supporting Information
Additional data and spectra.


Comments are not moderated before they are posted, but they can be removed by the site moderators if they are found to be in contravention of our Commenting Policy [opens in a new tab] - please read this policy before you post. Comments should be used for scholarly discussion of the content in question. You can find more information about how to use the commenting feature here [opens in a new tab] .
This site is protected by reCAPTCHA and the Google Privacy Policy [opens in a new tab] and Terms of Service [opens in a new tab] apply.