biostudies-literatureMcNeece AJUniversity of ChicagoDirectorate for Mathematical and Physical SciencesU.S. Department of DefenseArgonne National LaboratoryAlfred P. Sloan FoundationNational Institute of General Medical SciencesNIGMS NIH HHS3869-3872https://www.ebi.ac.uk/biostudies/studies/S-EPMC8058320biostudies-literatureUnknown57(32)Biology employs exquisite control over proton, electron, H-atom, or H<sub>2</sub> transfer. Similar control in synthetic systems has the potential to facilitate efficient and selective catalysis. Here we report a dihydrazonopyrrole Ni complex where an H<sub>2</sub> equivalent can be stored on the ligand periphery without metal-based redox changes and can be leveraged for catalytic hydrogenations. Kinetic and computational analysis suggests ligand hydrogenation proceeds by H<sub>2</sub> association followed by H-H scission. This complex is an unusual example where a synthetic system can mimic biology's ability to mediate H<sub>2</sub> transfer via secondary coordination sphere-based processes.Chemical communications (Cambridge, England)Catalytic hydrogenation enabled by ligand-based storage of hydrogen.PMC8058320DE-AC02-06CH11357FG 2019 1149700003765CHE-1834750R35 GM133470Jesse KASchneider JEMcNeece AJFilatov ASAnderson JSfalseCatalytic hydrogenation enabled by ligand-based storage of hydrogen.Biology employs exquisite control over proton, electron, H-atom, or H<sub>2</sub> transfer. Similar control in synthetic systems has the potential to facilitate efficient and selective catalysis. Here we report a dihydrazonopyrrole Ni complex where an H<sub>2</sub> equivalent can be stored on the ligand periphery without metal-based redox changes and can be leveraged for catalytic hydrogenations. Kinetic and computational analysis suggests ligand hydrogenation proceeds by H<sub>2</sub> association followed by H-H scission. This complex is an unusual example where a synthetic system can mimic biology's ability to mediate H<sub>2</sub> transfer via secondary coordination sphere-based processes.2021-01-01T00:00:00Z2021 Apr2025-04-04T10:17:11.046Z2025-04-04T10:17:11.046ZS-EPMC80583203372922110.1039/d0cc08236h