Abstract
Oxidation of H2 in a fuel cell converts the chemical energy of the H−H bond into electricity. Electrocatalytic oxidation of H2 by molecular catalysts typically requires one metal to perform multiple chemical steps: bind H2, heterolytically cleave H2, and then undergo two oxidation and two deprotonation steps. The electrocatalytic oxidation of H2 by a cooperative system using Cp*Cr(CO)3H and [Fe(diphosphine)(CO)3]+ has now been invetigated. A key step of the proposed mechanism is a rarely observed metal-to-metal hydrogen atom transfer from the Cr−H complex to the Fe, forming an Fe−H complex that is deprotonated and then oxidized electrochemically. This “division of chemical labor” features Cr interacting with H2 to cleave the H−H bond, while Fe interfaces with the electrode. Neither metal is required to heterolytically cleave H2, so this system provides a very unusual example of a homolytic reaction being a key step in a molecular electrocatalytic process.
| Original language | English |
|---|---|
| Pages (from-to) | 13523-13527 |
| Number of pages | 5 |
| Journal | Angewandte Chemie - International Edition |
| Volume | 57 |
| Issue number | 41 |
| DOIs | |
| Publication status | Published - Oct 8 2018 |
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Keywords
- electrocatalysis
- homolytic cleavage
- hydrides
- hydrogen atom transfer
- proton transfer
ASJC Scopus subject areas
- Catalysis
- Chemistry(all)
Cite this
H2 Oxidation Electrocatalysis Enabled by Metal-to-Metal Hydrogen Atom Transfer : A Homolytic Approach to a Heterolytic Reaction. / Chambers, Geoffrey M.; Wiedner, Eric; Bullock, R Morris.
In: Angewandte Chemie - International Edition, Vol. 57, No. 41, 08.10.2018, p. 13523-13527.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - H2 Oxidation Electrocatalysis Enabled by Metal-to-Metal Hydrogen Atom Transfer
T2 - A Homolytic Approach to a Heterolytic Reaction
AU - Chambers, Geoffrey M.
AU - Wiedner, Eric
AU - Bullock, R Morris
PY - 2018/10/8
Y1 - 2018/10/8
N2 - Oxidation of H2 in a fuel cell converts the chemical energy of the H−H bond into electricity. Electrocatalytic oxidation of H2 by molecular catalysts typically requires one metal to perform multiple chemical steps: bind H2, heterolytically cleave H2, and then undergo two oxidation and two deprotonation steps. The electrocatalytic oxidation of H2 by a cooperative system using Cp*Cr(CO)3H and [Fe(diphosphine)(CO)3]+ has now been invetigated. A key step of the proposed mechanism is a rarely observed metal-to-metal hydrogen atom transfer from the Cr−H complex to the Fe, forming an Fe−H complex that is deprotonated and then oxidized electrochemically. This “division of chemical labor” features Cr interacting with H2 to cleave the H−H bond, while Fe interfaces with the electrode. Neither metal is required to heterolytically cleave H2, so this system provides a very unusual example of a homolytic reaction being a key step in a molecular electrocatalytic process.
AB - Oxidation of H2 in a fuel cell converts the chemical energy of the H−H bond into electricity. Electrocatalytic oxidation of H2 by molecular catalysts typically requires one metal to perform multiple chemical steps: bind H2, heterolytically cleave H2, and then undergo two oxidation and two deprotonation steps. The electrocatalytic oxidation of H2 by a cooperative system using Cp*Cr(CO)3H and [Fe(diphosphine)(CO)3]+ has now been invetigated. A key step of the proposed mechanism is a rarely observed metal-to-metal hydrogen atom transfer from the Cr−H complex to the Fe, forming an Fe−H complex that is deprotonated and then oxidized electrochemically. This “division of chemical labor” features Cr interacting with H2 to cleave the H−H bond, while Fe interfaces with the electrode. Neither metal is required to heterolytically cleave H2, so this system provides a very unusual example of a homolytic reaction being a key step in a molecular electrocatalytic process.
KW - electrocatalysis
KW - homolytic cleavage
KW - hydrides
KW - hydrogen atom transfer
KW - proton transfer
UR - http://www.scopus.com/inward/record.url?scp=85053708065&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85053708065&partnerID=8YFLogxK
U2 - 10.1002/anie.201807510
DO - 10.1002/anie.201807510
M3 - Article
VL - 57
SP - 13523
EP - 13527
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
SN - 1433-7851
IS - 41
ER -