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Why Is There a Barrier in the Coupling of Two Radicals in the Water Oxidation Reaction?
KTH, School of Biotechnology (BIO), Theoretical Chemistry and Biology.
KTH, School of Biotechnology (BIO), Theoretical Chemistry and Biology.
KTH, School of Biotechnology (BIO), Theoretical Chemistry and Biology.ORCID iD: 0000-0002-1553-4027
2016 (English)In: ACS Catalysis, ISSN 2155-5435, E-ISSN 2155-5435, Vol. 6, no 12, p. 8308-8312Article in journal (Refereed) Published
Abstract [en]

Two radicals can form a bond without an energetic barrier. However, the radical coupling mechanism in ruthenium catalyzed water oxidation has been found to be associated with substantial activation energies. Here we have investigated the coupling reaction of [Ru=O(bda)L-2](+) catalysts with different axial L ligands. The interaction between the two oxo radical moieties at the Ru(V) state was found to have a favorable interaction in the transition state in comparison to the prereactive complex. To further understand the existence of the activation energy, the activation energy has been decomposed into distortion energy and interaction energy. No correlation between the experimental rates and the calculated coupling barriers of different axial L was found, showing that more aspects such as solvation, supramolecular properties, and solvent dynamics likely play important roles in the equilibrium between the free Ru-v=0 monomer and the [Ru-v=O center dot center dot center dot O=Ru-v] dimer. On the basis of our findings, we give general guidelines for the design of catalysts that operate by the radical coupling mechanism.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2016. Vol. 6, no 12, p. 8308-8312
Keywords [en]
water oxidation, radical coupling, I2M, DFT, bda, catalysis, ruthenium
National Category
Chemical Sciences
Identifiers
URN: urn:nbn:se:kth:diva-199489DOI: 10.1021/acscatal.6b02697ISI: 000389399400034OAI: oai:DiVA.org:kth-199489DiVA, id: diva2:1066998
Note

QC 20170119

Available from: 2017-01-19 Created: 2017-01-09 Last updated: 2017-11-29Bibliographically approved

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Fan, TingZhan, ShaoqiAhlquist, Mårten S. G.

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