A pendant proton shuttle on [Fe4N(CO)12]−alters product selectivity in formate vs. H2production via the hydride [H–Fe4N(CO)12]−

Loewen, Natalia D.; Thompson, Emily J.; Kagan, M.; Banales, Carolina L.; Myers, Thomas W.; Fettinger, James C.; Berben, Louise A.

doi:10.1039/c5sc03169a

Cited by 63 publications

(73 citation statements)

References 41 publications

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“…This opens the possibility to further employ 2 for the preparation of new clusters , . It is noteworthy that carbonyliron carbide and nitride clusters were recently found to be active for electrocatalysis , …”

Section: Discussionmentioning

confidence: 97%

Synthesis of the Highly Reduced [Fe₆C(CO)₁₅]^4– Carbonyl Carbide Cluster and Its Reactions with H⁺ and [Au(PPh₃)]⁺

et al. 2017

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The reduction of [Fe6C(CO)16]2– (1) with NaOH in DMSO or with Na/naphthalene in THF affords the highly reduced [Fe6C(CO)15]4– (2) monocarbide tetraanion. The molecular structure of 2 has been crystallographically determined as its [Et4N]4[Fe6C(CO)15]·CH3CN salt, revealing an octahedral structure as expected for a hexanuclear cluster possessing 86 valence electrons. The stepwise protonation of 2 with strong acids such as HBF4·Et2O results first in the monohydride trianion [HFe6C(CO)15]3– (3) and then the purported dihydride dianion [H2Fe6C(CO)15]2– (4), as indicated by 1H NMR spectroscopy. Both 3 and 4 are not stable enough to be isolated and rapidly decompose, yielding the parent dianion 1. The reaction of 2 with a slight excess of Au(PPh3)Cl affords the aurated dianion [Fe6C(CO)15(AuPPh3)2]2– (5), which has been isolated and structurally characterized as its [Et4N]2[Fe6C(CO)15(AuPPh3)2]·2CH3CN salt. DFT calculations allowed us to study, from a computational point of view, the electronic features of the new compounds and possible reaction intermediates.

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Section: Discussionmentioning

confidence: 97%

Synthesis of the Highly Reduced [Fe₆C(CO)₁₅]^4– Carbonyl Carbide Cluster and Its Reactions with H⁺ and [Au(PPh₃)]⁺

et al. 2017

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“…Still dealing with hydridation reactions, the observations made of the role of proton relays in the catalysis of the CO 2 ‐to‐formate electrochemical conversion are rather puzzling. In one case, introduction of a proton relay in the catalyst molecules deteriorates the selectivity in favor of H 2 evolution . In the other, the presence of a proton relay boosts the catalysis of the CO 2 ‐to‐formate conversion.…”

Section: Methodsmentioning

confidence: 99%

Proton Relays in Molecular Catalysis of Electrochemical Reactions: Origin and Limitations of the Boosting Effect

Savéant

2019

Angewandte Chemie

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Homogeneous catalysis of electrochemical reactions, related to contemporary energy challenges, often involves proton‐coupled electron transfer sequences. The idea rapidly emerged that installing the proton donor (for reductions, or acceptor for oxidations) inside the catalyst molecule should be beneficial in terms of efficiency, as it would then be closer to the nerve center of the process (usually the metal in the case of transition metal complex catalysts). If this proton relay has indeed done the job, it has lost its proton at the end of each catalytic loop, and must therefore be reprotonated (for reductions, or deprotonated for oxidations) from acid (or base) from the solution before a new catalytic loop can start. The impression may thus be that there is a zero‐sum game. The conditions under which this is not the case may entail, in contrast, a considerable boosting of catalysis. This will also allow explain why the proton is such a specifically appropriate agent for this task.

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“…In one case,i ntroduction of ap roton relay in the catalyst molecules deteriorates the selectivity in favor of H 2 evolution. [32] In the other, [33] the presence of aproton relay boosts the catalysis of the CO 2to-formate conversion.…”

mentioning

confidence: 99%

Proton Relays in Molecular Catalysis of Electrochemical Reactions: Origin and Limitations of the Boosting Effect

Savéant

2019

Angew Chem Int Ed

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Homogeneous catalysis of electrochemical reactions, related to contemporary energy challenges,o ften involves proton-coupled electron transfer sequences.T he idea rapidly emerged that installing the proton donor (for reductions,o r acceptor for oxidations) inside the catalyst molecule should be beneficial in terms of efficiency,asit would then be closer to the nerve center of the process (usually the metal in the case of transition metal complex catalysts). If this proton relay has indeed done the job,i th as lost its proton at the end of each catalytic loop,a nd must therefore be reprotonated (for reductions,o rd eprotonated for oxidations) from acid (or base) from the solution before an ew catalytic loop can start. The impression may thus be that there is azero-sum game.The conditions under which this is not the case may entail, in contrast, ac onsiderable boosting of catalysis.T his will also allowexplain why the proton is such aspecifically appropriate agent for this task.Supportinginformation (simplification of reactions schemes and detailed establishment of all the equations on which the above analysis is based) and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

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A pendant proton shuttle on [Fe₄N(CO)₁₂]⁻alters product selectivity in formate vs. H₂production via the hydride [H–Fe₄N(CO)₁₂]⁻

Abstract: A proton shuttle in the second coordination sphere of [Fe4N(CO)12]– promotes H2 evolution over formate formation from CO2.

Cited by 63 publications

References 41 publications

Synthesis of the Highly Reduced [Fe₆C(CO)₁₅]^4– Carbonyl Carbide Cluster and Its Reactions with H⁺ and [Au(PPh₃)]⁺

Synthesis of the Highly Reduced [Fe₆C(CO)₁₅]^4– Carbonyl Carbide Cluster and Its Reactions with H⁺ and [Au(PPh₃)]⁺

Proton Relays in Molecular Catalysis of Electrochemical Reactions: Origin and Limitations of the Boosting Effect

Proton Relays in Molecular Catalysis of Electrochemical Reactions: Origin and Limitations of the Boosting Effect

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A pendant proton shuttle on [Fe4N(CO)12]−alters product selectivity in formate vs. H2production via the hydride [H–Fe4N(CO)12]−

Abstract: A proton shuttle in the second coordination sphere of [Fe4N(CO)12]– promotes H2 evolution over formate formation from CO2.

Cited by 63 publications

References 41 publications

Synthesis of the Highly Reduced [Fe6C(CO)15]4– Carbonyl Carbide Cluster and Its Reactions with H+ and [Au(PPh3)]+

Synthesis of the Highly Reduced [Fe6C(CO)15]4– Carbonyl Carbide Cluster and Its Reactions with H+ and [Au(PPh3)]+

Proton Relays in Molecular Catalysis of Electrochemical Reactions: Origin and Limitations of the Boosting Effect

Proton Relays in Molecular Catalysis of Electrochemical Reactions: Origin and Limitations of the Boosting Effect

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A pendant proton shuttle on [Fe₄N(CO)₁₂]⁻alters product selectivity in formate vs. H₂production via the hydride [H–Fe₄N(CO)₁₂]⁻

Synthesis of the Highly Reduced [Fe₆C(CO)₁₅]^4– Carbonyl Carbide Cluster and Its Reactions with H⁺ and [Au(PPh₃)]⁺

Synthesis of the Highly Reduced [Fe₆C(CO)₁₅]^4– Carbonyl Carbide Cluster and Its Reactions with H⁺ and [Au(PPh₃)]⁺