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Ligand-Based H2 Transfer with Dihydrazonopyrrole Complexes of Nickel

preprint
submitted on 18.12.2020, 22:39 and posted on 21.12.2020, 13:17 by Andrew McNeece, Kate Jesse, Alexander S. Filatov, Joseph Schneider, John Anderson
Biology uses precise control over proton, electron, H-atom, or H2 transfer to mediate challenging reactivity. While synthetic complexes have made incredible strides in replicating secondary coordination electron or proton donors, there are comparatively fewer examples of ligands that can mediate both proton and electron storage. Rarer still are ligands that can store full H2 equivalents. Here we report a dihydrazonopyrrole Ni complex where an H2 equivalent can be stored on the ligand periphery without any redox change at the metal center. This ligand-based storage of H2 can be leveraged for catalytic hydrogenations. Kinetic and computational analysis suggests a rate determining H2 binding step followed by comparatively facile H–H scission to hydrogenate the ligand. This system is an unusual example where a synthetic system can mimic biology’s ability to mediate H2 transfer via secondary coordination sphere-based processes.

Funding

NIGMS R35 GM133470

3M NTFA

Sloan Foundation FG 2019 11497

NSF/CHE-1834750

DE-AC02-06CH11357

History

Email Address of Submitting Author

jsanderson@uchicago.edu

Institution

University of Chicago

Country

United States

ORCID For Submitting Author

0000-0002-0730-3018

Declaration of Conflict of Interest

None

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