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• W2321815683 endingPage "10311" @default.
• W2321815683 startingPage "10301" @default.
• W2321815683 abstract "The [FeFe]-hydrogenase enzymes catalyze hydrogen oxidation and production efficiently with binuclear Fe metal centers. Recently the bioinspired H2-producing model system Fe2(adt)(CO)2(dppv)2 (adt=azadithiolate and dppv=diphosphine) was synthesized and studied experimentally. In this system, the azadithiolate bridge facilitates the formation of a doubly protonated ammonium-hydride species through a proton relay. Herein computational methods are utilized to examine this system in the various oxidation states and protonation states along proposed mechanistic pathways for H2 production. The calculated results agree well with the experimental data for the geometries, CO vibrational stretching frequencies, and reduction potentials. The calculations illustrate that the NH···HFe dihydrogen bonding distance in the doubly protonated species is highly sensitive to the effects of ion-pairing between the ammonium and BF4– counterions, which are present in the crystal structure, in that the inclusion of BF4– counterions leads to a significantly longer dihydrogen bond. The non-hydride Fe center was found to be the site of reduction for terminal hydride species and unsymmetric bridging hydride species, whereas the reduced symmetric bridging hydride species exhibited spin delocalization between the Fe centers. According to both experimental measurements and theoretical calculations of the relative pKa values, the Fed center of the neutral species is more basic than the amine, and the bridging hydride species is more thermodynamically stable than the terminal hydride species. The calculations implicate a possible pathway for H2 evolution that involves an intermediate with H2 weakly bonded to one Fe, a short H2 distance similar to the molecular bond length, the spin density delocalized over the two Fe centers, and a nearly symmetrically bridged CO ligand. Overall, this study illustrates the mechanistic roles of the ammonium-hydride interaction, flexibility of the bridging CO ligand, and intramolecular electron transfer between the Fe centers in the catalytic cycle. Such insights will assist in the design of more effective bioinspired catalysts for H2 production." @default.
• W2321815683 created "2016-06-24" @default.
• W2321815683 creator A5005070123 @default.
• W2321815683 creator A5017273260 @default.
• W2321815683 creator A5041302371 @default.
• W2321815683 creator A5066027355 @default.
• W2321815683 date "2014-09-10" @default.
• W2321815683 modified "2023-10-12" @default.
• W2321815683 title "Computational Investigation of [FeFe]-Hydrogenase Models: Characterization of Singly and Doubly Protonated Intermediates and Mechanistic Insights" @default.
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• W2321815683 doi "https://doi.org/10.1021/ic5013523" @default.
• W2321815683 hasPubMedCentralId "https://www.ncbi.nlm.nih.gov/pmc/articles/4186672" @default.
• W2321815683 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/25207842" @default.
• W2321815683 hasPublicationYear "2014" @default.
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