Quantum Chemical Study of the Mechanism of Water Oxidation Catalyzed by a Heterotrinuclear Ru₂Mn Complex

Abstract

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Theoretical Insight into the Performance of MnII/III-Monosubstituted Heteropolytungstates as Water Oxidation Catalysts

“…In short, Mn IV –O • species 5 3 is capable of O–O bond formation and the barrier difference between WNA and oxo–oxo coupling mechanisms is only 2.9 kcal mol –1 , which indicates WNA and oxo–oxo coupling mechanisms are competitive. The result of the calculation is similar to the reports by the Siegbahn and Streb groups. − …”

Redox‐Active Ligand Assisted Catalytic Water Oxidation by a RuIV=O Intermediate

“…For the potentials of three steps of oxidation of [(L N5− )Ru III −OH] + , calculations at the PBE0‐GD3(BJ)/ma‐def2‐TZVP//PBE0‐GD3(BJ)/def2‐SVP level gave 0.09 V, 0.75 V, and 1.09 V, which fit the experimental values well. As spin analysis has been a powerful method in understanding the oxidation of metal complexes, Figure shows the optimized structures and spin populations of [(L N5− )Ru III −OH] + , [(L N5− )Ru IV =O] + , and [(L N5− ) +. Ru IV =O] 2+ , respectively.…”

“…Research Articles an 09 [93] .F or the potentials of three steps of oxidation of [(L N5À )Ru III À OH] + ,c alculations at the PBE0-GD3(BJ)/ma-def2-TZVP//PBE0-GD3(BJ)/def2-SVP [94][95][96][97][98] level gave 0.09 V, 0.75 V, and 1.09 V, which fit the experimental values well. As spin analysis has been ap owerful method in understanding the oxidation of metal complexes, [99,100] Fig [75] and [(tpy)(bpz)Ru II -OH 2 ] 2+ [74,77] do not show ligand oxidation when its Ru V = O form is compared to its Ru IV =Oanalogue.This process proves that L N5H is aredox-active ligand critical for the observed low overpotential.…”

Iron‐Catalyzed Water Oxidation: O–O Bond Formation via Intramolecular Oxo–Oxo Interaction

“…In 2‐TS1 , both O1 and O2 become the bridging ligands, which results in the formation of a hexa‐coordinated Fe1 and a hepta‐coordinated Fe2. From 2‐Int1 , O−O bond formation proceeds via the coupling of the two antiferromagnetically coupled oxo/oxyl groups ( 2‐TS2 , Figure 5), similarly to the pentanuclear iron catalyst, [12] and the heterotrinuclear MnRu 2 catalyst [26] . The barrier for 2‐TS2 was calculated to be 11.0 kcal mol −1 relative to 2‐Int1.…”