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Article

The Photochemistry of Fe2(S2C3H6)(CO)6(µ-CO) and Its Oxidized Form, Two Simple [FeFe]-Hydrogenase CO-Inhibited Models. A DFT and TDDFT Investigation

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Department of Biotechnology and Biosciences, University of Milano-Bicocca, 20126 Milan, Italy
2
Department of Earth and Environmental Sciences, University of Milano-Bicocca, 20126 Milan, Italy
*
Authors to whom correspondence should be addressed.
Academic Editor: Duncan Gregory
Inorganics 2021, 9(2), 16; https://doi.org/10.3390/inorganics9020016
Received: 5 January 2021 / Revised: 3 February 2021 / Accepted: 4 February 2021 / Published: 9 February 2021
(This article belongs to the Special Issue Cornerstones in Contemporary Inorganic Chemistry)
FeIFeI Fe2(S2C3H6)(CO)6(µ-CO) (1a–CO) and its FeIFeII cationic species (2a+–CO) are the simplest model of the CO-inhibited [FeFe] hydrogenase active site, which is known to undergo CO photolysis within a temperature-dependent process whose products and mechanism are still a matter of debate. Using density functional theory (DFT) and time-dependent density functional theory (TDDFT) computations, the ground state and low-lying excited-state potential energy surfaces (PESs) of 1a–CO and 2a+–CO have been explored aimed at elucidating the dynamics of the CO photolysis yielding Fe2(S2C3H6)(CO)6 (1a) and [Fe2(S2C3H6)(CO)6]+ (2a+), two simple models of the catalytic site of the enzyme. Two main results came out from these investigations. First, a–CO and 2a+–CO are both bound with respect to any CO dissociation with the lowest free energy barriers around 10 kcal mol−1, suggesting that at least 2a+–CO may be synthesized. Second, focusing on the cationic form, we found at least two clear excited-state channels along the PESs of 2a+–CO that are unbound with respect to equatorial CO dissociation. View Full-Text
Keywords: metal-carbonyl complexes; [FeFe]-hydrogenases; density functional theory; time-dependent DFT; organometallic photochemistry metal-carbonyl complexes; [FeFe]-hydrogenases; density functional theory; time-dependent DFT; organometallic photochemistry
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MDPI and ACS Style

Arrigoni, F.; Zampella, G.; De Gioia, L.; Greco, C.; Bertini, L. The Photochemistry of Fe2(S2C3H6)(CO)6(µ-CO) and Its Oxidized Form, Two Simple [FeFe]-Hydrogenase CO-Inhibited Models. A DFT and TDDFT Investigation. Inorganics 2021, 9, 16. https://doi.org/10.3390/inorganics9020016

AMA Style

Arrigoni F, Zampella G, De Gioia L, Greco C, Bertini L. The Photochemistry of Fe2(S2C3H6)(CO)6(µ-CO) and Its Oxidized Form, Two Simple [FeFe]-Hydrogenase CO-Inhibited Models. A DFT and TDDFT Investigation. Inorganics. 2021; 9(2):16. https://doi.org/10.3390/inorganics9020016

Chicago/Turabian Style

Arrigoni, Federica, Giuseppe Zampella, Luca De Gioia, Claudio Greco, and Luca Bertini. 2021. "The Photochemistry of Fe2(S2C3H6)(CO)6(µ-CO) and Its Oxidized Form, Two Simple [FeFe]-Hydrogenase CO-Inhibited Models. A DFT and TDDFT Investigation" Inorganics 9, no. 2: 16. https://doi.org/10.3390/inorganics9020016

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