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A computational study of the mechanism for water oxidation by (bpc)(bpy)(RuOH2)-O-II
KTH, School of Biotechnology (BIO), Theoretical Chemistry and Biology.
KTH, School of Biotechnology (BIO), Theoretical Chemistry and Biology.ORCID iD: 0000-0002-1553-4027
2014 (English)In: Dalton Transactions, ISSN 1477-9226, E-ISSN 1477-9234, Vol. 43, no 36, 13776-13782 p.Article in journal (Refereed) Published
Abstract [en]

A mechanistic study on the catalytic cycle water oxidation with 1 [(bpc)(bpy)(RuOH2)-O-II](+) (Hbpc = 2,2'-bipyridine-6-carboxylic acid, bpy = 2,2'-bipyridine) is described in this paper. Stepwise oxidation via proton-coupled electron transfer gives 3 [(bpc)(bpy)Ru-IV=O](+). An active 4 [(bpc)(bpy)Ru-V=O](2+), which is involved in the OO bond formation is generated from further 1e(-) oxidation of 3. Another different possible reaction at 4 was investigated and new destructive paths involving overoxidation of the metal were identified. The most viable path for OO bond formation via a water nucleophilic attack at the oxo of 4 is found to be the rate-determining step in this water oxidation catalytic cycle, and the hydro-peroxo 6 [(bpc)(bpy)-(RuOOH)-O-III](+) is generated accompanied with a proton transfer. The super-oxo 7(side-on) [(bpc)(bpy)(RuOO)-O-IV](+) and 8(side-on) [(bpc)(bpy)(RuOO)-O-V](2+), both low spin species, are generated by further oxidations of 6. Through an intersystem crossing they can transform to their high spin states, 9(end-on) [(bpc)(bpy)(RuOO)-O-IV](+) and 12(end-on) [(bpc)(bpy)(RuOO)-O-V](2+), respectively. Following a dissociative pathway O-2 is readily generated from both 9(end-on) and 12(end-on).

Place, publisher, year, edition, pages
2014. Vol. 43, no 36, 13776-13782 p.
National Category
Chemical Sciences
Identifiers
URN: urn:nbn:se:kth:diva-145657DOI: 10.1039/c4dt02113dISI: 000341282100035Scopus ID: 2-s2.0-84906302977OAI: oai:DiVA.org:kth-145657DiVA: diva2:719476
Note

Updated from manuscript to article in journal.

QC 20141009

Available from: 2014-05-26 Created: 2014-05-26 Last updated: 2017-12-05Bibliographically approved
In thesis
1. Theoretical Studies on Water Splitting Using Transition Metal Complexes
Open this publication in new window or tab >>Theoretical Studies on Water Splitting Using Transition Metal Complexes
2014 (English)Doctoral thesis, comprehensive summary (Other academic)
Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2014. xii, 66 p.
Series
TRITA-BIO-Report, ISSN 1654-2312 ; 2014:6
National Category
Theoretical Chemistry
Identifiers
urn:nbn:se:kth:diva-145191 (URN)978-91-7595-069-3 (ISBN)
Public defence
2014-06-13, Albanova FB53, Roslagstullsbacken 21, Stockholm, 10:00 (English)
Opponent
Supervisors
Note

QC 20140526

Available from: 2014-05-26 Created: 2014-05-14 Last updated: 2014-05-26Bibliographically approved

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Ahlquist, Mårten S. G.

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