Electrocatalytic Hydrogen Production by [Ni(7PPh2NH)2]2+: Removing the Distinction Between Endo- and Exo- Protonation Sites
Abstract
A new Ni(II) complex, [Ni(7PPh2NH)2]2+ (7PPh2NH = 3,6-triphenyl-1-aza-3,6-diphosphacycloheptane) has been synthesized, and its electrochemical properties are reported. The 7PPh2NH ligand features an NH, ensuring properly positioned protonated amine groups (N–H+) for electrocatalysis, regardless of whether protonation occurs exo- or endo- to the metal center. The compound is an electrocatalyst for H2 production in the presence of organic acids (pKa range 10–13 in CH3CN) with turnover frequencies ranging from 160–770 s-1 at overpotentials between 320–470 mV, as measured at the half peak potential of the catalytic wave. In stark contrast to [Ni(PR2NR'2)2]2+ and other [Ni(7PPh2NR')]2+ complexes, catalytic turnover frequencies for H2 production by [Ni(7PPh2NH)2]2+ do not show catalytic rate enhancement upon the addition of H2O. This finding supports the assertion that [Ni(7PPh2NH)2]2+ eliminates the distinction between the endo- and exo-protonation isomers. This research was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences. Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy.
- Authors:
- Publication Date:
- Research Org.:
- Energy Frontier Research Centers (EFRC) (United States). Center for Molecular Electrocatalysis (CME); Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1182863
- Report Number(s):
- PNNL-SA-104339
KC0307010
- DOE Contract Number:
- AC05-76RL01830
- Resource Type:
- Journal Article
- Journal Name:
- ACS Catalysis, 5(4):2116-2123
- Additional Journal Information:
- Journal Name: ACS Catalysis, 5(4):2116-2123
- Country of Publication:
- United States
- Language:
- English
- Subject:
- nickel phosphine; electrocatalyst; proton movement; hydrogen production
Citation Formats
Brown, Houston JS, Wiese, Stefan, Roberts, John A., Bullock, R. Morris, and Helm, Monte L. Electrocatalytic Hydrogen Production by [Ni(7PPh2NH)2]2+: Removing the Distinction Between Endo- and Exo- Protonation Sites. United States: N. p., 2015.
Web. doi:10.1021/cs502132y.
Brown, Houston JS, Wiese, Stefan, Roberts, John A., Bullock, R. Morris, & Helm, Monte L. Electrocatalytic Hydrogen Production by [Ni(7PPh2NH)2]2+: Removing the Distinction Between Endo- and Exo- Protonation Sites. United States. https://doi.org/10.1021/cs502132y
Brown, Houston JS, Wiese, Stefan, Roberts, John A., Bullock, R. Morris, and Helm, Monte L. 2015.
"Electrocatalytic Hydrogen Production by [Ni(7PPh2NH)2]2+: Removing the Distinction Between Endo- and Exo- Protonation Sites". United States. https://doi.org/10.1021/cs502132y.
@article{osti_1182863,
title = {Electrocatalytic Hydrogen Production by [Ni(7PPh2NH)2]2+: Removing the Distinction Between Endo- and Exo- Protonation Sites},
author = {Brown, Houston JS and Wiese, Stefan and Roberts, John A. and Bullock, R. Morris and Helm, Monte L.},
abstractNote = {A new Ni(II) complex, [Ni(7PPh2NH)2]2+ (7PPh2NH = 3,6-triphenyl-1-aza-3,6-diphosphacycloheptane) has been synthesized, and its electrochemical properties are reported. The 7PPh2NH ligand features an NH, ensuring properly positioned protonated amine groups (N–H+) for electrocatalysis, regardless of whether protonation occurs exo- or endo- to the metal center. The compound is an electrocatalyst for H2 production in the presence of organic acids (pKa range 10–13 in CH3CN) with turnover frequencies ranging from 160–770 s-1 at overpotentials between 320–470 mV, as measured at the half peak potential of the catalytic wave. In stark contrast to [Ni(PR2NR'2)2]2+ and other [Ni(7PPh2NR')]2+ complexes, catalytic turnover frequencies for H2 production by [Ni(7PPh2NH)2]2+ do not show catalytic rate enhancement upon the addition of H2O. This finding supports the assertion that [Ni(7PPh2NH)2]2+ eliminates the distinction between the endo- and exo-protonation isomers. This research was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences. Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy.},
doi = {10.1021/cs502132y},
url = {https://www.osti.gov/biblio/1182863},
journal = {ACS Catalysis, 5(4):2116-2123},
number = ,
volume = ,
place = {United States},
year = {Fri Apr 03 00:00:00 EDT 2015},
month = {Fri Apr 03 00:00:00 EDT 2015}
}
Works referenced in this record:
Powering the planet: Chemical challenges in solar energy utilization
journal, October 2006
- Lewis, N. S.; Nocera, D. G.
- Proceedings of the National Academy of Sciences, Vol. 103, Issue 43, p. 15729-15735
Solar Energy Supply and Storage for the Legacy and Nonlegacy Worlds
journal, November 2010
- Cook, Timothy R.; Dogutan, Dilek K.; Reece, Steven Y.
- Chemical Reviews, Vol. 110, Issue 11
Earth-abundant hydrogen evolution electrocatalysts
journal, January 2014
- McKone, James R.; Marinescu, Smaranda C.; Brunschwig, Bruce S.
- Chem. Sci., Vol. 5, Issue 3
Mimicking hydrogenases: From biomimetics to artificial enzymes
journal, July 2014
- Simmons, Trevor R.; Berggren, Gustav; Bacchi, Marine
- Coordination Chemistry Reviews, Vol. 270-271
Synthetic Models for the Active Site of the [FeFe]-Hydrogenase: Catalytic Proton Reduction and the Structure of the Doubly Protonated Intermediate
journal, November 2012
- Carroll, Maria E.; Barton, Bryan E.; Rauchfuss, Thomas B.
- Journal of the American Chemical Society, Vol. 134, Issue 45
Development of Molecular Electrocatalysts for Energy Storage
journal, February 2014
- DuBois, Daniel L.
- Inorganic Chemistry, Vol. 53, Issue 8
Beyond the Active Site: The Impact of the Outer Coordination Sphere on Electrocatalysts for Hydrogen Production and Oxidation
journal, June 2014
- Ginovska-Pangovska, Bojana; Dutta, Arnab; Reback, Matthew L.
- Accounts of Chemical Research, Vol. 47, Issue 8
Production of hydrogen by electrocatalysis: making the H–H bond by combining protons and hydrides
journal, January 2014
- Bullock, R. Morris; Appel, Aaron M.; Helm, Monte L.
- Chem. Commun., Vol. 50, Issue 24
Structure/Function Relationships of [NiFe]- and [FeFe]-Hydrogenases
journal, October 2007
- Fontecilla-Camps, Juan C.; Volbeda, Anne; Cavazza, Christine
- Chemical Reviews, Vol. 107, Issue 10
Structural and Functional Analogues of the Active Sites of the [Fe]-, [NiFe]-, and [FeFe]-Hydrogenases †
journal, June 2009
- Tard, Cédric; Pickett, Christopher J.
- Chemical Reviews, Vol. 109, Issue 6
Investigating and Exploiting the Electrocatalytic Properties of Hydrogenases
journal, October 2007
- Vincent, Kylie A.; Parkin, Alison; Armstrong, Fraser A.
- Chemical Reviews, Vol. 107, Issue 10, p. 4366-4413
Hydrogenases
journal, March 2014
- Lubitz, Wolfgang; Ogata, Hideaki; Rüdiger, Olaf
- Chemical Reviews, Vol. 114, Issue 8
Hydrogenases: Hydrogen-Activating Enzymes
journal, March 2002
- Frey, Michel
- ChemBioChem, Vol. 3, Issue 2-3
Conformational Mobility and Pendent Base Effects on Electrochemistry of Synthetic Analogues of the [FeFe]-Hydrogenase Active Site
journal, May 2014
- Crouthers, Danielle J.; Denny, Jason A.; Bethel, Ryan D.
- Organometallics, Vol. 33, Issue 18
Synthesis and Electrochemical Studies of Cobalt(III) Monohydride Complexes Containing Pendant Amines
journal, August 2013
- Wiedner, Eric S.; Roberts, John A. S.; Dougherty, William G.
- Inorganic Chemistry, Vol. 52, Issue 17
An iron complex with pendent amines as a molecular electrocatalyst for oxidation of hydrogen
journal, February 2013
- Liu, Tianbiao; DuBois, Daniel L.; Bullock, R. Morris
- Nature Chemistry, Vol. 5, Issue 3
Iron Complexes for the Electrocatalytic Oxidation of Hydrogen: Tuning Primary and Secondary Coordination Spheres
journal, March 2014
- Darmon, Jonathan M.; Raugei, Simone; Liu, Tianbiao
- ACS Catalysis, Vol. 4, Issue 4
Heterolytic cleavage of H 2 by bifunctional manganese( i ) complexes: impact of ligand dynamics, electrophilicity, and base positioning
journal, January 2014
- Hulley, Elliott B.; Helm, Monte L.; Bullock, R. Morris
- Chem. Sci., Vol. 5, Issue 12
A modular, energy-based approach to the development of nickel containing molecular electrocatalysts for hydrogen production and oxidation
journal, August 2013
- Shaw, Wendy J.; Helm, Monte L.; DuBois, Daniel L.
- Biochimica et Biophysica Acta (BBA) - Bioenergetics, Vol. 1827, Issue 8-9
Abundant Metals Give Precious Hydrogenation Performance
journal, November 2013
- Bullock, R. M.
- Science, Vol. 342, Issue 6162
A Synthetic Nickel Electrocatalyst with a Turnover Frequency Above 100,000 s-1 for H2 Production
journal, August 2011
- Helm, M. L.; Stewart, M. P.; Bullock, R. M.
- Science, Vol. 333, Issue 6044, p. 863-866
High Catalytic Rates for Hydrogen Production Using Nickel Electrocatalysts with Seven-Membered Cyclic Diphosphine Ligands Containing One Pendant Amine
journal, February 2013
- Stewart, Michael P.; Ho, Ming-Hsun; Wiese, Stefan
- Journal of the American Chemical Society, Vol. 135, Issue 16
Proton Delivery and Removal in [Ni(P R 2 N R ′ 2 ) 2 ] 2+ Hydrogen Production and Oxidation Catalysts
journal, November 2012
- O’Hagan, Molly; Ho, Ming-Hsun; Yang, Jenny Y.
- Journal of the American Chemical Society, Vol. 134, Issue 47
Moving Protons with Pendant Amines: Proton Mobility in a Nickel Catalyst for Oxidation of Hydrogen
journal, September 2011
- O’Hagan, Molly; Shaw, Wendy J.; Raugei, Simone
- Journal of the American Chemical Society, Vol. 133, Issue 36, p. 14301-14312
1,3,6-Azadiphosphacycloheptanes: A novel type of heterocyclic diphosphines
journal, March 2008
- Karasik, Andrey A.; Balueva, Anna S.; Moussina, Elvira I.
- Heteroatom Chemistry, Vol. 19, Issue 2
[Ni(P Ph 2 N C6H4X 2 ) 2 ] 2+ Complexes as Electrocatalysts for H 2 Production: Effect of Substituents, Acids, and Water on Catalytic Rates
journal, April 2011
- Kilgore, Uriah J.; Roberts, John A. S.; Pool, Douglas H.
- Journal of the American Chemical Society, Vol. 133, Issue 15
Studies of a Series of [Ni(P R 2 N Ph 2 ) 2 (CH 3 CN)] 2+ Complexes as Electrocatalysts for H 2 Production: Substituent Variation at the Phosphorus Atom of the P 2 N 2 Ligand
journal, November 2011
- Kilgore, Uriah J.; Stewart, Michael P.; Helm, Monte L.
- Inorganic Chemistry, Vol. 50, Issue 21
Theory of Stationary Electrode Polarography. Single Scan and Cyclic Methods Applied to Reversible, Irreversible, and Kinetic Systems.
journal, April 1964
- Nicholson, R. S.; Shain, Irving
- Analytical Chemistry, Vol. 36, Issue 4, p. 706-723
Catalysis of chemical reactions by electrodes
journal, September 1980
- Saveant, Jean Michel
- Accounts of Chemical Research, Vol. 13, Issue 9
Direct Determination of Equilibrium Potentials for Hydrogen Oxidation/Production by Open Circuit Potential Measurements in Acetonitrile
journal, June 2012
- Roberts, John A. S.; Bullock, R. Morris
- Inorganic Chemistry, Vol. 52, Issue 7
Determining the Overpotential for a Molecular Electrocatalyst
journal, December 2013
- Appel, Aaron M.; Helm, Monte L.
- ACS Catalysis, Vol. 4, Issue 2
Stabilization of Nickel Complexes with Ni 0 ···H–N Bonding Interactions Using Sterically Demanding Cyclic Diphosphine Ligands
journal, December 2011
- Wiedner, Eric S.; Yang, Jenny Y.; Chen, Shentan
- Organometallics, Vol. 31, Issue 1
Self-Consistent Spectrophotometric Basicity Scale in Acetonitrile Covering the Range between Pyridine and DBU
journal, September 2000
- Kaljurand, Ivari; Rodima, Toomas; Leito, Ivo
- The Journal of Organic Chemistry, Vol. 65, Issue 19
Extension of the Self-Consistent Spectrophotometric Basicity Scale in Acetonitrile to a Full Span of 28 p K a Units: Unification of Different Basicity Scales
journal, February 2005
- Kaljurand, Ivari; Kütt, Agnes; Sooväli, Lilli
- The Journal of Organic Chemistry, Vol. 70, Issue 3
Titration of bases in acetonitrile
journal, November 1967
- Kolthoff, Izaak M.; Chantooni, Miran K.; Bhowmik, Sadhana.
- Analytical Chemistry, Vol. 39, Issue 13