Journal
INORGANICA CHIMICA ACTA
Volume 424, Issue -, Pages 150-155Publisher
ELSEVIER SCIENCE SA
DOI: 10.1016/j.ica.2014.07.046
Keywords
Sulfide oxygenation; Hydrogen peroxide; Diruthenium(II,III); Diruthenium(III,III); Stepwise reaction
Categories
Funding
- Purdue University
- US Army Research Office [DAAD 190110708, W911NF-06-1-0305]
- US National Science Foundation [CHE 1057621]
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [1057621] Funding Source: National Science Foundation
Ask authors/readers for more resources
Diruthenium(II,III) tetracarboxylates, Ru-2(OAc)(4)Cl (A), Ru-2(esp)(2)Cl (B, esp = tetramethyl-1,3-benzenedipropionate) and Ru-2(3-HB)(4)Cl (C, 3-HB = 3-hydroxybenzoate) were investigated for activating hydrogen peroxide in organic sulfide oxygenation. The speciation of the substrate and potential products, sulfoxide and sulfone, were investigated for each catalyst. With methyl phenyl sulfide as the substrate, A simultaneously produces sulfoxide and sulfone, B yields the highest turnover with complete conversion to sulfoxide at 6 min before sulfone appears, and C facilitates complete conversion to sulfoxide in 20 min but little subsequent conversion to sulfone. The dependence of the initial reaction rate on catalyst and H2O2 concentrations were investigated. A small set of other sulfides were subjected to catalytic reactions with C, and all reactions resulted in near quantitative conversion. Finally, the sulfide oxygenation activity and stability towards hydrogen peroxide of the diphosphonate complex Na-4[Ru-2(hedp)(2)(H2O)Cl] (D, hedp = 1-hydroxyethylidenediphosphonate) was investigated, and D was found to be an effective catalyst, which retains its activity over an extended period of time due to its robustness at the (III, III) oxidation state. (C) 2014 Elsevier B.V. All rights reserved.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available