Achieving Reversible H2/H+ Interconversion at Room Temperature with Enzyme-Inspired Molecular Complexes: A Mechanistic Study

Priyadarshani, Nilusha; Dutta, Arnab; Ginovska-Pangovska, Bojana; Buchko, Garry W.; O'Hagan, Molly J.; Raugei, Simone; Shaw, Wendy J.

doi:10.1021/acscatal.6b01433

Title: Achieving Reversible H2/H+ Interconversion at Room Temperature with Enzyme-Inspired Molecular Complexes: A Mechanistic Study

Journal Article · Fri Sep 02 00:00:00 EDT 2016 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.6b01433· OSTI ID:1322506

Priyadarshani, Nilusha; Dutta, Arnab; Ginovska-Pangovska, Bojana; Buchko, Garry W.; O'Hagan, Molly J.; Raugei, Simone; Shaw, Wendy J.

Inspired by the contribution of the protein scaffold to the efficiency with which enzymes function, we report the first molecular complex that is reversible for electrocatalytic H2 production/oxidation at room temperature in methanol. [Ni(PCy2NPhe2)2]2+ (CyPhe; PR2NR’2 = 1,5-diaza-3,7-diphosphacyclooctane, Cy=cyclohexyl, Phe=phenylalanine), shows reversible behavior in acidic methanol with peripheral phenylalanine groups providing key contributions to the catalytic behavior. The importance of the aromatic rings is implicated in achieving reversibility, based on the lack of reversibility of similar complexes, [Ni(PCy2NAmino Acid2)2]2+, containing arginine (CyArg) or glycine (CyGly). A complex with an added OH group on the ring, (CyTyr; Tyr=Tyrosine), also shows similar behavior. NMR studies reveal a significantly slower rate of chair-boat isomerization for the CyPhe relative to other derivatives, suggesting that the aromatic groups provide structural control by interacting with each other, an observation supported by molecular dynamics studies. NMR studies also show extremely fast proton movement, with a proton pathway from the Ni-H through the pendant amine to the –COOH group. Further, studies of acomplex without the –COOH group, [Ni(PCy2NTym2)2]2+ (CyTym; Tym=Tyramine), are not reversible and have slow proton movement from the pendant amine, demonstrating the essential nature of the –COOH group in achieving reversibility. Finally, methanol is demonstrated to play a critical contributing role. The influence of multiple factors on reversibility for this synthetic catalyst is a demonstration of the intricate interplay between the first, second, and outer coordination spheres and resembles the complexity observed in metalloenzymes.

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Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States). Environmental Molecular Sciences Laboratory (EMSL)

Sponsoring Organization:: USDOE

DOE Contract Number:: AC05-76RL01830

OSTI ID:: 1322506

Report Number(s):: PNNL-SA-115312; 44681; KC0302010

Journal Information:: ACS Catalysis, Vol. 6, Issue 9; ISSN 2155-5435

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

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