The synthesis, characterization, and protonation of [Fe2(CO)6{(μ-SCH2)2(Et)P= O}] (1) using the moderately strong acid CF3CO2H (pKaMeCN = 12.7) are reported. Digital simulations of the cyclic voltammetry of 1 in the presence of CF3CO2H and DFT calculations have allowed us to obtain a detailed mechanistic picture of the processes underlying the catalytic hydrogen evolution reaction (HER) that 1 can mediate. Moreover, DFT has shed light on the role of the P= O functionality in the whole catalytic cycle of proton reduction. The reductive behavior of 1 features a double electron transfer with potential inversion, which is associated with deep structural rearrangement of the catalyst. The double reduction appears also functional to the intramolecular proton transfer from the P= O group to the diiron core, a crucial process for the H+/H- heterocoupling yielding H2. The key intermediate for the H2 formation and release is predicted to be a 3H+/3e- species, in which P= O is perfectly poised to shuttle protons from solution to the Fe-H-Fe moiety. Therefore, the R-P= O bridgehead installed in a dithiolato linker of a diiron core proves a valid and versatile alternative to the natural nitrogen-based Fe2 strap.

Almazahreh, L., Arrigoni, F., Abul-Futouh, H., El-Khateeb, M., Gorls, H., Elleouet, C., et al. (2021). Proton Shuttle Mediated by (SCH2)2P= O Moiety in [FeFe]-Hydrogenase Mimics: Electrochemical and DFT Studies. ACS CATALYSIS, 11(12), 7080-7098 [10.1021/acscatal.0c05563].

Proton Shuttle Mediated by (SCH2)2P= O Moiety in [FeFe]-Hydrogenase Mimics: Electrochemical and DFT Studies

Arrigoni F.;Bertini L.;De Gioia L.;Zampella G.
;
2021

Abstract

The synthesis, characterization, and protonation of [Fe2(CO)6{(μ-SCH2)2(Et)P= O}] (1) using the moderately strong acid CF3CO2H (pKaMeCN = 12.7) are reported. Digital simulations of the cyclic voltammetry of 1 in the presence of CF3CO2H and DFT calculations have allowed us to obtain a detailed mechanistic picture of the processes underlying the catalytic hydrogen evolution reaction (HER) that 1 can mediate. Moreover, DFT has shed light on the role of the P= O functionality in the whole catalytic cycle of proton reduction. The reductive behavior of 1 features a double electron transfer with potential inversion, which is associated with deep structural rearrangement of the catalyst. The double reduction appears also functional to the intramolecular proton transfer from the P= O group to the diiron core, a crucial process for the H+/H- heterocoupling yielding H2. The key intermediate for the H2 formation and release is predicted to be a 3H+/3e- species, in which P= O is perfectly poised to shuttle protons from solution to the Fe-H-Fe moiety. Therefore, the R-P= O bridgehead installed in a dithiolato linker of a diiron core proves a valid and versatile alternative to the natural nitrogen-based Fe2 strap.
Articolo in rivista - Articolo scientifico
biomimetic compound; cyclic voltammetry; DFT; hydrogen; hydrogenase; phosphine oxide; protonation; sulfur;
English
7080
7098
19
Almazahreh, L., Arrigoni, F., Abul-Futouh, H., El-Khateeb, M., Gorls, H., Elleouet, C., et al. (2021). Proton Shuttle Mediated by (SCH2)2P= O Moiety in [FeFe]-Hydrogenase Mimics: Electrochemical and DFT Studies. ACS CATALYSIS, 11(12), 7080-7098 [10.1021/acscatal.0c05563].
Almazahreh, L; Arrigoni, F; Abul-Futouh, H; El-Khateeb, M; Gorls, H; Elleouet, C; Schollhammer, P; Bertini, L; De Gioia, L; Rudolph, M; Zampella, G; Weigand, W
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/10281/322981
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