Hydroperoxo group

B3LYP calculations as described in Section 2. b Structures optimized with a 6-31 G(d) basis for the main group elements. c Also alkylperoxo complexes. d Attack of Oa of the hydroperoxo (alkylperoxo) group.e Attack of OP of the hydroperoxo group. 

An interesting square molecule with mixed bridges was obtained as the result of oxidative C-CN bond cleavage in benzylnitrile (172). The dinuclear cation [Cu°2(PD 0)(OOH)] + contains the active hydroperoxo group that attacks... 

The spectral changes are consistent with, but do not prove the formation of, a transient alkylhydroperoxide derivative of, the Ve cage (replacement of a p-oxo bridge with an alkyl hydroperoxo group), which might be the catalytic species. While only 4 turnovers are observed, the reaction is evidently catalytic, as the reaction does not proceed in the absence of catalyst on the same time scale. Efforts are underway to isolate and fully characterize this lower-symmetry vanadium-containing specie(s). 

The iron(II) precatalysts are generally oxidized by H2O2 or oxygen transfer agents such as iodosylbenzene (PhIO, see Scheme 6.2), but alkylhydroperox-ides, peracids, oxone, N2O, XO (X = C1, Br), ozone, dioxygen, and Ce in aqueous solution have also been used [12c, 34]. The H20, oxidation of the iron(II) precursors with the pentadentate ligands and in methanol at low temperature leads to metastable Fe intermediates which were spectroscopically characterized the -based system with the hydroperoxo group trans to N7 is. 

A nucleophilic attack by a hydroxide on a coordinated ethylene, as shown by reaction 2.3.4.1, is the key step in the manufacture of acetaldehyde by the Wacker process (see Section 8.2). In reaction 2.3.4.2, the high oxidation state of titanium makes the coordinated oxygen atom of an organic hydroperoxo group sufficiently electrophilic for it to be... 

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