Synergistic Effect of Pendant N Moieties for Proton Shuttling in the Dehydrogenation of Formic Acid Catalyzed by Biomimetic IrIII Complexes

Formic acid (FA) is among the most promising hydrogen storage materials. The development of efficient catalysts for the dehydrogenation of FA via molecular‐level control and precise tuning remains challenging. A series of biomimetic Ir complexes was developed for the efficient dehydrogenation of FA...

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Veröffentlicht in:ChemSusChem 2020-09, Vol.13 (18), p.5015-5022
Hauptverfasser: Wang, Wan‐Hui, Wang, Hong, Yang, Yajing, Lai, Xiaoling, Li, Yang, Wang, Jiasheng, Himeda, Yuichiro, Bao, Ming
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Sprache:eng
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Zusammenfassung:Formic acid (FA) is among the most promising hydrogen storage materials. The development of efficient catalysts for the dehydrogenation of FA via molecular‐level control and precise tuning remains challenging. A series of biomimetic Ir complexes was developed for the efficient dehydrogenation of FA in an aqueous solution without base addition. A high turnover frequency of 46510 h−1 was achieved at 90 °C in 1 m FA solution with complex 1 bearing pendant pyridine. Experimental and mechanistic studies revealed that the integrated pendant pyridine and pyrazole moieties of complex 1 could act as proton relay and facilitate proton shuttling in the outer coordination sphere. This study provides a new strategy to control proton transfer accurately and a new principle for the design of efficient catalysts for FA dehydrogenation. Shuttle service: Experimental and computational studies indicate that pendant pyridine and NH moieties of pyrazole can enhance the formic acid dehydrogenation cooperatively by facilitating proton shuttling to the metal center.
ISSN:1864-5631
1864-564X
DOI:10.1002/cssc.202001190