Preprint Article Version 1 Preserved in Portico This version is not peer-reviewed

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

Version 1 : Received: 24 January 2021 / Approved: 25 January 2021 / Online: 25 January 2021 (11:43:03 CET)

A peer-reviewed article of this Preprint also exists.

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. 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.

Journal reference: Inorganics 2021, 9, 16
DOI: 10.3390/inorganics9020016

Abstract

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 lowest free energy barriers around 10 kcal mol-1, suggesting that at least 2a+-CO might be synthetized. 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.

Subject Areas

Metal-carbonyl complexes; [FeFe]-hydrogenases; density functional theory; time-dependent DFT; organometallic photochemistry

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