Ligand Noninnocence in Nickel Porphyrins: Nickel Isobacteriochlorin Formation under Hydrogen Evolution Conditions

Maher, Andrew G.; Liu, Mengran; Nocera, Daniel G.

doi:10.1021/acs.inorgchem.9b00717

Title: Ligand Noninnocence in Nickel Porphyrins: Nickel Isobacteriochlorin Formation under Hydrogen Evolution Conditions

Journal Article · 30 May 2019 · Inorganic Chemistry

DOI: https://doi.org/10.1021/acs.inorgchem.9b00717 · OSTI ID:1597839

Maher, Andrew G. ^[1]; Liu, Mengran ^[1];

^[1]

Harvard Univ., Cambridge, MA (United States)

Here, an electron-deficient nickel porphyrin complex undergoes facile ring reduction to form a nickel isobacteriochlorin complex under hydrogen evolution conditions. Spectroscopic experiments indicate that the reduced nickel porphyrin undergoes subsequent reduction and protonation to form a phlorin anion rather than a metal hydride, demonstrating that the key initial proton-coupled electron transfer step is directed toward the ligand versus the metal. The phlorin anion facilely converts to the isobacteriochlorin in the presence of two-electron and three-proton equivalents. Cyclic voltammetry (CV) and spectroscopic experiments reveal that the four-electron, four-proton electrochemical reduction of nickel porphyrin to isobacteriochlorin occurs promptly in the presence of the strong proton donor tosic acid, followed by hydrogen evolution reaction (HER) catalysis at slightly more negative potentials. CVs of independently synthesized Ni isobacteriochlorin show a catalytic HER at the same potentials as those observed for the HER in CVs of the Ni porphyrin. We discover that, under strongly acidic conditions, the HER catalysis arises from conversion of the Ni isobacteriochlorin into a nickel-containing, catalytically active electrode-adsorbed species. These results show that Ni porphyrin converts to Ni isobacteriochlorin under HER catalysis conditions via a ligand-based PCET process and that it is the isobacteriochlorin complex which gives rise to an active HER catalysis.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Harvard Univ., Cambridge, MA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division

Grant/Contract Number:: SC0017619

OSTI ID:: 1597839

Alternate ID(s):: OSTI ID: 1992623

Journal Information:: Inorganic Chemistry, Vol. 58, Issue 12; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (59)

Powering the planet: Chemical challenges in solar energy utilization Lewis, N. S.; Nocera, D. G. Proceedings of the National Academy of Sciences, Vol. 103, Issue 43, p. 15729-15735 https://doi.org/10.1073/pnas.0603395103	journal	October 2006
Chemistry of Personalized Solar Energy Nocera, Daniel G. Inorganic Chemistry, Vol. 48, Issue 21 https://doi.org/10.1021/ic901328v	journal	November 2009
Solar Energy Supply and Storage for the Legacy and Nonlegacy Worlds Cook, Timothy R.; Dogutan, Dilek K.; Reece, Steven Y. Chemical Reviews, Vol. 110, Issue 11 https://doi.org/10.1021/cr100246c	journal	November 2010
Proton-Coupled Electron Transfer Cukier, Robert I.; Nocera, Daniel G. Annual Review of Physical Chemistry, Vol. 49, Issue 1 https://doi.org/10.1146/annurev.physchem.49.1.337	journal	October 1998
PROTON-COUPLED ELECTRON TRANSFER: A Reaction Chemist's View Mayer, James M. Annual Review of Physical Chemistry, Vol. 55, Issue 1 https://doi.org/10.1146/annurev.physchem.55.091602.094446	journal	June 2004
Proton-Coupled Electron Transfer Huynh, My Hang V.; Meyer, Thomas J. Chemical Reviews, Vol. 107, Issue 11 https://doi.org/10.1021/cr0500030	journal	November 2007
Electrochemical Approach to the Mechanistic Study of Proton-Coupled Electron Transfer Costentin, Cyrille Chemical Reviews, Vol. 108, Issue 7 https://doi.org/10.1021/cr068065t	journal	July 2008
Theory of Proton-Coupled Electron Transfer in Energy Conversion Processes Hammes-Schiffer, Sharon Accounts of Chemical Research, Vol. 42, Issue 12 https://doi.org/10.1021/ar9001284	journal	December 2009
Electrocatalytic Hydrogen Evolution at Low Overpotentials by Cobalt Macrocyclic Glyoxime and Tetraimine Complexes Hu, Xile; Brunschwig, Bruce S.; Peters, Jonas C. Journal of the American Chemical Society, Vol. 129, Issue 29 https://doi.org/10.1021/ja067876b	journal	July 2007
Hydrogen Evolution Catalyzed by Cobaloximes Dempsey, Jillian L.; Brunschwig, Bruce S.; Winkler, Jay R. Accounts of Chemical Research, Vol. 42, Issue 12 https://doi.org/10.1021/ar900253e	journal	December 2009
Hydrogen Evolution Catalyzed by Cobalt Diimine–Dioxime Complexes Kaeffer, Nicolas; Chavarot-Kerlidou, Murielle; Artero, Vincent Accounts of Chemical Research, Vol. 48, Issue 5 https://doi.org/10.1021/acs.accounts.5b00058	journal	May 2015
The roles of the first and second coordination spheres in the design of molecular catalysts for H ₂ production and oxidation Rakowski DuBois, M.; DuBois, Daniel L. Chem. Soc. Rev., Vol. 38, Issue 1 https://doi.org/10.1039/B801197B	journal	January 2009
A Synthetic Nickel Electrocatalyst with a Turnover Frequency Above 100,000 s^-1 for H₂ Production Helm, M. L.; Stewart, M. P.; Bullock, R. M. Science, Vol. 333, Issue 6044, p. 863-866 https://doi.org/10.1126/science.1205864	journal	August 2011
A Cobalt–Dithiolene Complex for the Photocatalytic and Electrocatalytic Reduction of Protons McNamara, William R.; Han, Zhiji; Alperin, Paul J. Journal of the American Chemical Society, Vol. 133, Issue 39 https://doi.org/10.1021/ja207842r	journal	October 2011
Small molecule mimics of hydrogenases: hydrides and redox Gloaguen, Frédéric; Rauchfuss, Thomas B. Chem. Soc. Rev., Vol. 38, Issue 1 https://doi.org/10.1039/B801796B	journal	January 2009
Catalysts made of earth-abundant elements (Co, Ni, Fe) for water splitting: Recent progress and future challenges Du, Pingwu; Eisenberg, Richard Energy & Environmental Science, Vol. 5, Issue 3 https://doi.org/10.1039/c2ee03250c	journal	January 2012
“Hangman” Porphyrins for the Assembly of a Model Heme Water Channel Yeh, Chen-Yu; Chang, Christopher J.; Nocera, Daniel G. Journal of the American Chemical Society, Vol. 123, Issue 7 https://doi.org/10.1021/ja003245k	journal	February 2001
Efficient Synthesis of Hangman Porphyrins Dogutan, Dilek K.; Bediako, D. Kwabena; Teets, Thomas S. Organic Letters, Vol. 12, Issue 5 https://doi.org/10.1021/ol902947h	journal	March 2010
Nature of hydrogen interactions with Ni(II) complexes containing cyclic phosphine ligands with pendant nitrogen bases Wilson, A. D.; Shoemaker, R. K.; Miedaner, A. Proceedings of the National Academy of Sciences, Vol. 104, Issue 17 https://doi.org/10.1073/pnas.0608928104	journal	March 2007
Influence of a Pendant Amine in the Second Coordination Sphere on Proton Transfer at a Dissymmetrically Disubstituted Diiron System Related to the [2Fe] _H Subsite of [FeFe]H ₂ ase Ezzaher, Salah; Capon, Jean-François; Gloaguen, Frédéric Inorganic Chemistry, Vol. 48, Issue 1 https://doi.org/10.1021/ic801369u	journal	December 2008
Factors Determining the Rate and Selectivity of 4e ^– /4H ⁺ Electrocatalytic Reduction of Dioxygen by Iron Porphyrin Complexes Chatterjee, Sudipta; Sengupta, Kushal; Mondal, Biswajit Accounts of Chemical Research, Vol. 50, Issue 7 https://doi.org/10.1021/acs.accounts.7b00192	journal	July 2017
Activating Fe(I) Porphyrins for the Hydrogen Evolution Reaction Using Second-Sphere Proton Transfer Residues Rana, Atanu; Mondal, Biswajit; Sen, Pritha Inorganic Chemistry, Vol. 56, Issue 4 https://doi.org/10.1021/acs.inorgchem.6b01707	journal	February 2017
Computational Study of Anomalous Reduction Potentials for Hydrogen Evolution Catalyzed by Cobalt Dithiolene Complexes Solis, Brian H.; Hammes-Schiffer, Sharon Journal of the American Chemical Society, Vol. 134, Issue 37 https://doi.org/10.1021/ja306857q	journal	September 2012
Proton–hydride tautomerism in hydrogen evolution catalysis Quintana, Luis M. Aguirre; Johnson, Samantha I.; Corona, Sydney L. Proceedings of the National Academy of Sciences, Vol. 113, Issue 23 https://doi.org/10.1073/pnas.1606018113	journal	May 2016
Role of Ligand Protonation in Dihydrogen Evolution from a Pentamethylcyclopentadienyl Rhodium Catalyst Johnson, Samantha I.; Gray, Harry B.; Blakemore, James D. Inorganic Chemistry, Vol. 56, Issue 18 https://doi.org/10.1021/acs.inorgchem.7b01698	journal	September 2017
Metal-Assisted Ligand-Centered Electrocatalytic Hydrogen Evolution upon Reduction of a Bis(thiosemicarbazonato)Cu(II) Complex Haddad, Andrew Z.; Cronin, Steve P.; Mashuta, Mark S. Inorganic Chemistry, Vol. 56, Issue 18 https://doi.org/10.1021/acs.inorgchem.7b01608	journal	August 2017
Control of Ligand p K _a Values Tunes the Electrocatalytic Dihydrogen Evolution Mechanism in a Redox-Active Aluminum(III) Complex Sherbow, Tobias J.; Fettinger, James C.; Berben, Louise A. Inorganic Chemistry, Vol. 56, Issue 15 https://doi.org/10.1021/acs.inorgchem.7b00230	journal	April 2017
Theoretical Analysis of Cobalt Hangman Porphyrins: Ligand Dearomatization and Mechanistic Implications for Hydrogen Evolution Solis, Brian H.; Maher, Andrew G.; Honda, Tatsuhiko ACS Catalysis, Vol. 4, Issue 12 https://doi.org/10.1021/cs501454y	journal	November 2014
Nickel phlorin intermediate formed by proton-coupled electron transfer in hydrogen evolution mechanism Solis, Brian H.; Maher, Andrew G.; Dogutan, Dilek K. Proceedings of the National Academy of Sciences, Vol. 113, Issue 3 https://doi.org/10.1073/pnas.1521834112	journal	December 2015
Singly versus Doubly Reduced Nickel Porphyrins for Proton Reduction: Experimental and Theoretical Evidence for a Homolytic Hydrogen-Evolution Reaction Han, Yongzhen; Fang, Huayi; Jing, Huize Angewandte Chemie, Vol. 128, Issue 18 https://doi.org/10.1002/ange.201510001	journal	March 2016
The Photoreduction of Porphyrins: Structure of the Products Mauzerall, D. Journal of the American Chemical Society, Vol. 84, Issue 12 https://doi.org/10.1021/ja00871a032	journal	June 1962
Negative Ions of Porphin Metal Complexes Closs, G. L.; Closs, L. E. Journal of the American Chemical Society, Vol. 85, Issue 6 https://doi.org/10.1021/ja00889a038	journal	March 1963
Electrochemical studies of some porphyrin IX derivatives in aprotic media Wilson, George S.; Peychal-Heiling, Gerald. Analytical Chemistry, Vol. 43, Issue 4 https://doi.org/10.1021/ac60299a003	journal	April 1971
Chemistry of porphyrins. IV. Behavior of di- and tetrahydroporphyrins under alkaline conditions. Direct observation of the chlorin-phlorin equilibrium Whitlock, H. W.; Oester, M. Y. Journal of the American Chemical Society, Vol. 95, Issue 17 https://doi.org/10.1021/ja00798a049	journal	August 1973
Synthetic Chlorins, Possible Surrogates for Chlorophylls, Prepared by Derivatization of Porphyrins Taniguchi, Masahiko; Lindsey, Jonathan S. Chemical Reviews, Vol. 117, Issue 2 https://doi.org/10.1021/acs.chemrev.5b00696	journal	March 2016
Evidence for photosensitised hydrogen production from water in the absence of precious metals, redox-mediators and co-catalysts Salzl, S.; Ertl, M.; Knör, G. Physical Chemistry Chemical Physics, Vol. 19, Issue 12 https://doi.org/10.1039/C6CP07725K	journal	January 2017
Unusual Stability of a Bacteriochlorin Electrocatalyst under Reductive Conditions. A Case Study on CO ₂ Conversion to CO Jiang, Jianbing; Matula, Adam J.; Swierk, John R. ACS Catalysis, Vol. 8, Issue 11 https://doi.org/10.1021/acscatal.8b02991	journal	September 2018
Synthesis and Characterization of meso -Substituted Cobalt Tetradehydrocorrin and Evaluation of Its Electrocatalytic Behavior Toward CO ₂ Reduction and H ₂ Evolution Ogawa, Ayumu; Oohora, Koji; Hayashi, Takashi Inorganic Chemistry, Vol. 57, Issue 23 https://doi.org/10.1021/acs.inorgchem.8b02333	journal	November 2018
Boron-Capped Tris(glyoximato) Cobalt Clathrochelate as a Precursor for the Electrodeposition of Nanoparticles Catalyzing H ₂ Evolution in Water Anxolabéhère-Mallart, Elodie; Costentin, Cyrille; Fournier, Maxime Journal of the American Chemical Society, Vol. 134, Issue 14 https://doi.org/10.1021/ja301134e	journal	March 2012
Cobalt-Based Particles Formed upon Electrocatalytic Hydrogen Production by a Cobalt Pyridine Oxime Complex Ghachtouli, Sanae El; Guillot, Regis; Brisset, Francois ChemSusChem, Vol. 6, Issue 12 https://doi.org/10.1002/cssc.201300564	journal	October 2013
Cobalt-Bisglyoximato Diphenyl Complex as a Precatalyst for Electrocatalytic H ₂ Evolution Anxolabéhère-Mallart, Elodie; Costentin, Cyrille; Fournier, Maxime The Journal of Physical Chemistry C, Vol. 118, Issue 25 https://doi.org/10.1021/jp500813r	journal	June 2014
A nickel dimethyl glyoximato complex to form nickel based nanoparticles for electrocatalytic H ₂ production Cherdo, Stéphanie; Ghachtouli, Sanae El; Sircoglou, Marie Chem. Commun., Vol. 50, Issue 88 https://doi.org/10.1039/C4CC05355A	journal	January 2014
Electrode initiated proton-coupled electron transfer to promote degradation of a nickel( ii ) coordination complex McCarthy, Brian D.; Donley, Carrie L.; Dempsey, Jillian L. Chemical Science, Vol. 6, Issue 5 https://doi.org/10.1039/C5SC00476D	journal	January 2015
Digital simulations on unequally spaced grids. Rudolph, Manfred Journal of Electroanalytical Chemistry, Vol. 543, Issue 1 https://doi.org/10.1016/S0022-0728(02)01257-3	journal	February 2003
Halogen photoelimination from dirhodium phosphazane complexes via chloride-bridged intermediates Powers, David C.; Chambers, Matthew B.; Teets, Thomas S. Chemical Science, Vol. 4, Issue 7 https://doi.org/10.1039/c3sc50462j	journal	January 2013
Chemical Redox Agents for Organometallic Chemistry Connelly, Neil G.; Geiger, William E. Chemical Reviews, Vol. 96, Issue 2 https://doi.org/10.1021/cr940053x	journal	January 1996
Pentakis(trifluoromethyl)phenyl, a Sterically Crowded and Electron-withdrawing Group: Synthesis and Acidity of Pentakis(trifluoromethyl)benzene, -toluene, -phenol, and -aniline Kütt, Agnes; Movchun, Valeria; Rodima, Toomas The Journal of Organic Chemistry, Vol. 73, Issue 7 https://doi.org/10.1021/jo702513w	journal	April 2008
Reductive chemistry of nickel hydroporphyrins. Evidence for a biologically significant difference between porphyrins, hydroporphyrins, and other tetrapyrroles Stolzenberg, Alan M.; Stershic, Matthew T. Journal of the American Chemical Society, Vol. 110, Issue 19 https://doi.org/10.1021/ja00227a020	journal	September 1988
Electrochemical and Spectroelectrochemical Studies of Diphosphorylated Metalloporphyrins. Generation of a Phlorin Anion Product Fang, Yuanyuan; Gorbunova, Yulia G.; Chen, Ping Inorganic Chemistry, Vol. 54, Issue 7 https://doi.org/10.1021/acs.inorgchem.5b00067	journal	March 2015
Role of pendant proton relays and proton-coupled electron transfer on the hydrogen evolution reaction by nickel hangman porphyrins Bediako, D. Kwabena; Solis, Brian H.; Dogutan, Dilek K. Proceedings of the National Academy of Sciences, Vol. 111, Issue 42 https://doi.org/10.1073/pnas.1414908111	journal	October 2014
Coordination-Induced Spin-State Switching with Nickel Chlorin and Nickel Isobacteriochlorin Dommaschk, Marcel; Thoms, Vanessa; Schütt, Christian Inorganic Chemistry, Vol. 54, Issue 19 https://doi.org/10.1021/acs.inorgchem.5b01756	journal	August 2015
Facile Formation of Hexahydroporphyrin Complexes by Reduction of Octaethylisobacteriochlorinnickel(II) Lahiri, Goutam K.; Stolzenberg, Alan M. Angewandte Chemie International Edition in English, Vol. 32, Issue 3 https://doi.org/10.1002/anie.199304291	journal	March 1993
Origin of the Regioselective Reduction of Chlorins Bruhn, Torsten; Brückner, Christian The Journal of Organic Chemistry, Vol. 80, Issue 10 https://doi.org/10.1021/acs.joc.5b00137	journal	March 2015
Stable iso-bacteriochlorin mimics from porpholactone: effect of a β-oxazolone moiety on the frontier π-molecular orbitals Yu, Yi; Furuyama, Taniyuki; Tang, Juan Inorganic Chemistry Frontiers, Vol. 2, Issue 7 https://doi.org/10.1039/C5QI00054H	journal	January 2015
Elements of Molecular and Biomolecular Electrochemistry Savéant, Jean-Michel https://doi.org/10.1002/0471758078	book	January 2006
F430 model chemistry. Mechanistic investigation of the reduction, coupling, and dehydrohalogenation of alkyl halides by the nickel(I) octaethylisobacteriochlorin anion Lahiri, Goutam K.; Schussel, Leonard J.; Stolzenberg, Alan M. Inorganic Chemistry, Vol. 31, Issue 24 https://doi.org/10.1021/ic00050a016	journal	November 1992
Siroheme: A New Prosthetic Group Participating in Six-Electron Reduction Reactions Catalyzed by Both Sulfite and Nitrite Reductases Murphy, M. J.; Siegel, L. M.; Tove, S. R. Proceedings of the National Academy of Sciences, Vol. 71, Issue 3 https://doi.org/10.1073/pnas.71.3.612	journal	March 1974
Discovery and Synthesis of Less Common Natural Hydroporphyrins Montforts, Franz-Peter; Gerlach, Benjamin; Hoeper, Frank Chemical Reviews, Vol. 94, Issue 2 https://doi.org/10.1021/cr00026a003	journal	March 1994
Metalloenzymes of the nitrate-reducing system Losada, M. Journal of Molecular Catalysis, Vol. 1, Issue 4 https://doi.org/10.1016/0304-5102(76)80013-2	journal	May 1976

Cited By (1)

Boosting hydrogen evolution by using covalent frameworks of fluorinated cobalt porphyrins supported on carbon nanotubes Xu, Gelun; Lei, Haitao; Zhou, Guojun Chemical Communications, Vol. 55, Issue 84 https://doi.org/10.1039/c9cc06916j	journal	January 2019

Similar Records

Hangman Catalysis for Photo–and Photoelectro–Chemical Activation of Water Proton-Coupled Electron Transfer Mechanisms of Small Molecule Activation

Technical Report · 2013 · OSTI ID:1367667

Nocera, Daniel G.

Nickel catalysis of olefin epoxidation

Journal Article · 1987 · Inorg. Chem.; (United States) · OSTI ID:6630434

Koola, J D; Kochi, J K

Nickel phlorin intermediate formed by proton-coupled electron transfer in hydrogen evolution mechanism

Journal Article · 2015 · Proceedings of the National Academy of Sciences of the United States of America · OSTI ID:1235503

Solis, Brian H.; Maher, Andrew G.; Dogutan, Dilek K.; +2 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
anions
evolution reactions
macrocycles
pyrroles
redox reactions

Title: Ligand Noninnocence in Nickel Porphyrins: Nickel Isobacteriochlorin Formation under Hydrogen Evolution Conditions

Citation Formats

References (59)

Cited By (1)

Similar Records

Related Subjects