We found a match
Your institution may have access to this item. Find your institution then sign in to continue.
- Title
Oxygenation by Ruthenium Monosubstituted Polyoxotungstates in Aqueous Solution: Experimental and Computational Dissection of a Ru(III)-Ru(V) Catalytic Cycle.
- Authors
Sartorel, Andrea; Miró, Pere; Carraro, Mauro; Berardi, Serena; Bortolini, Olga; Bagno, Alessandro; Bo , Carles; Bonchio, Marcella
- 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 RuIII 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)-μ-peroxo-POM dimeric intermediate has been accessed by density functional theory. This observation indicates a new landmark for tracing POM-based manifolds for multiredox oxygen reduction/activation, where metal-centered oxygenated species play a pivotal role.
- Subjects
RUTHENIUM; PLATINUM group; POLYOXOTUNGSTATES; POLYOXOMETALATES; AQUEOUS solutions
- Publication
Chemistry - A European Journal, 2014, Vol 20, Issue 35, p10932
- ISSN
0947-6539
- Publication type
Article
- DOI
10.1002/chem.201404088