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Catalytic hydrogenation enabled by ligand-based storage of hydrogen.


ABSTRACT: Biology employs exquisite control over proton, electron, H-atom, or H2 transfer. Similar control in synthetic systems has the potential to facilitate efficient and selective catalysis. Here we report a dihydrazonopyrrole Ni complex where an H2 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 H2 association followed by H-H scission. This complex is an unusual example where a synthetic system can mimic biology's ability to mediate H2 transfer via secondary coordination sphere-based processes.

SUBMITTER: McNeece AJ 

PROVIDER: S-EPMC8058320 | biostudies-literature | 2021 Apr

REPOSITORIES: biostudies-literature

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Catalytic hydrogenation enabled by ligand-based storage of hydrogen.

McNeece Andrew J AJ   Jesse Kate A KA   Filatov Alexander S AS   Schneider Joseph E JE   Anderson John S JS  

Chemical communications (Cambridge, England) 20210317 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> associati  ...[more]

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