Ligand Noninnocence in Nickel Porphyrins: Nickel Isobacteriochlorin Formation under Hydrogen Evolution Conditions
Abstract
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 4-electron, 4-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 catalytic HER at the same potentials as that observed for HER in CVs of the Ni porphyrin. We find 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 that gives rise to an active HER catalysis.
- Publication Date:
- Research Org.:
- Harvard Univ., Cambridge, MA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
- OSTI Identifier:
- 1597839
- Alternate Identifier(s):
- OSTI ID: 1992623
- Grant/Contract Number:
- SC0017619
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Inorganic Chemistry
- Additional Journal Information:
- Journal Volume: 58; Journal Issue: 12; Journal ID: ISSN 0020-1669
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; anions; evolution reactions; macrocycles; pyrroles; redox reactions
Citation Formats
Maher, Andrew G., Liu, Mengran, and Nocera, Daniel G. Ligand Noninnocence in Nickel Porphyrins: Nickel Isobacteriochlorin Formation under Hydrogen Evolution Conditions. United States: N. p., 2019.
Web. doi:10.1021/acs.inorgchem.9b00717.
Maher, Andrew G., Liu, Mengran, & Nocera, Daniel G. Ligand Noninnocence in Nickel Porphyrins: Nickel Isobacteriochlorin Formation under Hydrogen Evolution Conditions. United States. https://doi.org/10.1021/acs.inorgchem.9b00717
Maher, Andrew G., Liu, Mengran, and Nocera, Daniel G. Thu .
"Ligand Noninnocence in Nickel Porphyrins: Nickel Isobacteriochlorin Formation under Hydrogen Evolution Conditions". United States. https://doi.org/10.1021/acs.inorgchem.9b00717. https://www.osti.gov/servlets/purl/1597839.
@article{osti_1597839,
title = {Ligand Noninnocence in Nickel Porphyrins: Nickel Isobacteriochlorin Formation under Hydrogen Evolution Conditions},
author = {Maher, Andrew G. and Liu, Mengran and Nocera, Daniel G.},
abstractNote = {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 4-electron, 4-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 catalytic HER at the same potentials as that observed for HER in CVs of the Ni porphyrin. We find 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 that gives rise to an active HER catalysis.},
doi = {10.1021/acs.inorgchem.9b00717},
journal = {Inorganic Chemistry},
number = 12,
volume = 58,
place = {United States},
year = {Thu May 30 00:00:00 EDT 2019},
month = {Thu May 30 00:00:00 EDT 2019}
}
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