Journal article
Oxygenation by Ruthenium Monosubstituted Polyoxotungstates in Aqueous Solution: Experimental and Computational Dissection of a Ru(III)-Ru(V) Catalytic Cycle
Chemistry : a European journal, Vol.20(35), pp.10932-10943
08/25/2014
DOI: 10.1002/chem.201404088
PMID: 25113582
Abstract
Molecular polyoxometalates with one embedded ruthenium center, with general formula [RuII/III-( DMSO)XW11O39](n-) (X = P, Si; n = 4-6), are readily synthesized in gram scale under microwave irradiation by a flash hydrothermal protocol. These nanodimensional and polyanionic complexes enable aerobic oxygenation in water. Catalytic oxygen transfer to dimethylsulfoxide (DMSO) yielding the corresponding sulfone (DMSO2) has been investigated with a combined kinetic, spectroscopic and computational approach addressing: (i) the Ru-III catalyst resting state; (ii) the bimolecular event dictating its transformation in the rate-determining step; (iii) its aerobic evolution to a high-valent ruthenium oxene species; (iv) the terminal fate to diamagnetic dimers. This pathway is reminiscent of natural heme systems and of bioinspired artificial porphyrins. The in silico characterization of a key bis-Ru(IV)-mu-peroxo-POM dimeric intermediate has been accessed by density functional theory. This observation indicates a new landmark for tracing POMbased manifolds for multiredox oxygen reduction/activation, where metal-centered oxygenated species play a pivotal role.
Details
- Title: Subtitle
- Oxygenation by Ruthenium Monosubstituted Polyoxotungstates in Aqueous Solution: Experimental and Computational Dissection of a Ru(III)-Ru(V) Catalytic Cycle
- Creators
- Andrea Sartorel - University of PaduaPere Miro - Institut Català d'Investigació QuímicaMauro Carraro - University of PaduaSerena Berardi - University of PaduaOlga Bortolini - University of FerraraAlessandro Bagno - University of PaduaCarles Bo - Universidad Rovira i VirgiliMarcella Bonchio - Institut Català d'Investigació Química
- Resource Type
- Journal article
- Publication Details
- Chemistry : a European journal, Vol.20(35), pp.10932-10943
- Publisher
- Wiley
- DOI
- 10.1002/chem.201404088
- PMID
- 25113582
- ISSN
- 0947-6539
- eISSN
- 1521-3765
- Number of pages
- 12
- Grant note
- European Social Fund; European Social Fund (ESF) RBAP11C58Y / Italian MIUR(FIRB "NanoSolar"); Ministry of Education, Universities and Research (MIUR) CTQ2011-29054-C02-02 / Spanish Ministerio de Economia y Competitividad (MINECO) ICIQ Foundation; Foundation CELLEX University and Enterprise Department of Catalan Government 2010N3T9M4_001 / Italian MIUR (PRIN "Hi-Phuture"); Ministry of Education, Universities and Research (MIUR) CTQ2008-06549-CO2- 02/BQU; CTQ2004-03346/PPQ; CSD2006-0003 / MICINN of the Government of Spain University and Research Commission of Innovation 2009SGR-00259; 2009FIC00026 / Generalitat de Catalunya; General Electric SGR01-00315; 2005SGR00715; 2005SGR00104 / CIRIT of the Catalan Government Fondazione Cariparo (Nanomode-progetti di eccellenza); Fondazione Cariparo
- Language
- English
- Date published
- 08/25/2014
- Academic Unit
- Chemistry
- Record Identifier
- 9984618638002771
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