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Hydrolytic Stability and Hydrogen Peroxide Activation of Zirconium‐Based Oxoclusters
Author(s) -
Faccioli Francesco,
Bauer Matthias,
Pedron Danilo,
Sorarù Antonio,
Carraro Mauro,
Gross Silvia
Publication year - 2015
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201402767
Subject(s) - chemistry , sulfone , catalysis , hydrogen peroxide , x ray photoelectron spectroscopy , acetonitrile , sulfide , sulfoxide , zirconium , inorganic chemistry , hydrolysis , extended x ray absorption fine structure , fourier transform infrared spectroscopy , raman spectroscopy , reactivity (psychology) , nuclear chemistry , absorption spectroscopy , polymer chemistry , organic chemistry , medicine , physics , alternative medicine , quantum mechanics , pathology , optics , nuclear magnetic resonance
The hydrolytic stability of [Zr 6 (OH) 4 O 4 {O(O)CC(CH 3 )=CH 2 } 12 ] (Zr 6 ), and [Zr 6 O 4 (OH) 4 {O(O)CCH 2 CH=CH 2 } 12 ] 2 · 6[CH 2 =CHCH 2 C(O)OH] (Zr 12 ) oxoclusters in different environments was thoroughly investigated by FTIR, Raman, and X‐ray photoelectron spectroscopy (XPS). Specific information about the local structures around the Zr centers during the stability tests was achieved by in situ extended X‐ray absorption fine structure (EXAFS) measurements, and the exact compositions were determined by inductively coupled plasma MS (ICP‐MS) and elemental analysis. By this multidimensional spectroscopic approach, an overview on the structures formed after different treatments could be gained. The stability of the oxoclusters was then investigated in the presence of hydrogen peroxide, and the formation of peroxo–metal complexes was detected. Thus, a kinetic study was performed in acetonitrile to evaluate the performances of the oxoclusters as oxygen transfer catalysts. The oxidation of methyl p ‐tolyl sulfide to the corresponding sulfoxide and sulfone was chosen as a model reaction; in some cases, an interesting selectivity towards the formation of the sulfone was found over more than 4700 catalytic cycles.