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Stepovik, L. P.; Martinova, I. M.; Dodonov, V. A.; Cherkasov, V. K.

doi:10.1023/a:1015812016868

Cited by 11 publications

(23 citation statements)

References 12 publications

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“…When a solvent has reactive C-H bonds (ethylbenzene and cumene), signals of adducts of the solvent peroxy radicals with PBN are observed apart from the latter signal, that is, homolysis of 6 triggers free radical processes that involve the solvent. The identification of all types of O-centered radicals that can arise upon homolysis of trioxide 6 confirms its formation in the oxidative system "aluminum tert-butoxide-tert-butyl peroxide" and the possibility of trioxide decomposition at both peroxide bonds 211 .…”

Section: Aluminum Tert-butoxide As a Source Of Trioxidementioning

confidence: 61%

“…In later publications 210,211 , the authors presented more evidence supporting this hypothesis. Homolysis of the peroxide bond is a typical reaction of all trioxides.…”

Section: Aluminum Tert-butoxide As a Source Of Trioxidementioning

confidence: 82%

“…Indeed, decomposition of 6 was found to give a full possible set of O-centered radicals. The formation of free radicals was studied by ESR using spin traps: 2-methyl-2-nitrosopropane (MNP) and C-phenyl-N-tert-butylnitrone (PBN) 211 . In the absence of spin traps, a broad nonresolved singlet was recorded in benzene or chlorobenzene.…”

Section: Aluminum Tert-butoxide As a Source Of Trioxidementioning

confidence: 99%

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Peroxide intermediates of oxidation processes: Organic trioxides

Khursan

2014

Patai's Chemistry of Functional Groups

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The review discusses the results of studies on the chemistry of organic trioxides ROOOR (R = H or an organic radical) carried out in the past years. The spectral identification, structure, thermal stability and chemical properties of HOOOH, HOOO ⋅ , hydrotrioxides, open‐chain and cyclic trioxides (including fullerene ozonides) are described. The significance of trioxides for biochemistry, environmental chemistry, and organic synthesis is much higher than it was believed previously. The chemical reactions that these compounds undergo resemble those of peroxides. However, the temperature range in which trioxide reactions occur is shifted considerably towards low temperatures. Homolytic decomposition at one of the OO bonds is the most typical reaction of trioxides. Trioxides are liable to induced and catalytic decomposition. Hydrotrioxides demonstrate high oxidative activity. Decomposition of some trioxides is accompanied by efficient generation of singlet oxygen.

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Section: Aluminum Tert-butoxide As a Source Of Trioxidementioning

confidence: 61%

“…In later publications 210,211 , the authors presented more evidence supporting this hypothesis. Homolysis of the peroxide bond is a typical reaction of all trioxides.…”

Section: Aluminum Tert-butoxide As a Source Of Trioxidementioning

confidence: 82%

Section: Aluminum Tert-butoxide As a Source Of Trioxidementioning

confidence: 99%

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Peroxide intermediates of oxidation processes: Organic trioxides

Khursan

2014

Patai's Chemistry of Functional Groups

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“…The fact that best oxidized are C3H bonds in the allyl, benzyl, and benzhydryl radicals points to a homolytic nature of the processes. The formation of carboncentered and peroxyl radicals from the substrates was confirmed by ESR [6]. At present we are searching for new mild oxidants comprising other metals, both maingroup and transition.…”

mentioning

confidence: 89%

“…The reaction between the components of the systems involves formation of Ti(IV) peroxide and trioxide, like in the system comprising aluminum alkoxide [6,8]. Decomposition of the trioxide results in oxygen evolution (therewith, Ti(IV) alkoxide is regenerated [7]) and formation of oxygen-centered alkoxyl and peroxyl radicals [Scheme (2)].…”

mentioning

confidence: 99%

Titanium(IV) tert-Butoxide-tert-Butyl Hydroperoxide System as Oxidant for C-H Bonds in Hydrocarbons and Oxygen-containing Compounds

2005

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The system Ti(IV) tetra-tert-butoxide3tert-butyl hydroperoxide in mild conditions (20oC) oxidizes C3H bonds of methyl (toluene), methylene (hexane, ethylbenzene, benzyl ethyl ether), and methine (1,1-diphenylethane, triphenylmethane) groups. The role of oxidant is played by the oxygen generated by the system. The process involves free radicals and produces hydroperoxides and Ti(IV) peroxides. The latter decompose both with preservation and decomposition of the hydrocarbon skeleton.Previously we showed [135] that the Al(OBu-t)33 t-BuOOH system effectively and in mild conditions (20oC) oxidizes C3H bonds in alkanes, alkylarenes, as well as oxygen-containing functional derivatives (aldehydes, ketones, saturated ethers and esters, etc.). The fact that best oxidized are C3H bonds in the allyl, benzyl, and benzhydryl radicals points to a homolytic nature of the processes. The formation of carboncentered and peroxyl radicals from the substrates was confirmed by ESR [6]. At present we are searching for new mild oxidants comprising other metals, both maingroup and transition. Therewith, we set ourselves the task to establish the role of the metal, common features of the processes, and reaction centers on the system and substrates.It is known that aluminum and Ti(IV) alkoxides sometimes exhibit similar chemical properties. Thus, their reactions with alcohols, carbonyl compounds, and carboxylic acid anhydrides and halides occur in a similar fashion. Both metals have vacant p and d orbitals. Therefore, one may expect that reactions of aluminum and Ti(IV) alkoxides will similarly react with hydroperoxides. The aim of the present work was to explore the oxidative power of the Ti(IV) tetra-tertbutoxide (I)3tert-butyl hydroperoxide (II) system. The ÄÄÄÄÄÄÄÄÄÄÄÄ reaction of alkoxide I with hydroperoxide II in a 1 : 2 ratio in benzene at room temperature is accompanied by evolution of oxygen whose yield attains 0.853 0.90 mol/mol I [7]. Distillation after reaction completion recovered~0.80 mol of Ti(IV) alkoxide [Eq. (1)].Ti(OBu-t) 4 + 2t-BuOOH,(1)When the I : II ratio was increased to 1 : 10, the yield of oxygen was 4.2 mol. No solvent oxidation products were found.The reaction between the components of the systems involves formation of Ti(IV) peroxide and trioxide, like in the system comprising aluminum alkoxide [6,8]. Decomposition of the trioxide results in oxygen evolution (therewith, Ti(IV) alkoxide is regenerated [7]) and formation of oxygen-centered alkoxyl and peroxyl radicals [Scheme (2)].(t-BuO) 4 + t-BuOOH 76 47 t-BuOH + (t-BuO) 3 TiOOBu-t, (t-BuO) 3 TiOOBu-t + t-BuOOH t-BuOH + (t-BuO) 3 TiOOOBu-t.

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Catalytic Epoxidations with Peroxides: Molybdenum Trioxide Species as the Origin of Allylic Byproducts

Neuenschwander

Meier

Hermans

2012

Chemistry A European J

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Molybdenum(VI)peroxide species, formed in the reaction of Mo(VI) complexes with peroxides, are able to epoxidize >C=C< double bonds heterolytically. In this study, theoretical and experimental evidence is provided for a kinetically competing reaction reaction of such molybdenum(VI)peroxide species with additional peroxide reagent, leading to molybdenum(VI)trioxide species, which easily decompose into radicals. Under epoxidation conditions, those radicals will reduce the selectivity, due to the formation of allylic byproducts. The involved reaction pathways are characterized by DFT calculations, providing kinetic parameters that are in good agreement with the experimental observations.

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Cited by 11 publications

References 12 publications

Peroxide intermediates of oxidation processes: Organic trioxides

Peroxide intermediates of oxidation processes: Organic trioxides

Titanium(IV) tert-Butoxide-tert-Butyl Hydroperoxide System as Oxidant for C-H Bonds in Hydrocarbons and Oxygen-containing Compounds

Catalytic Epoxidations with Peroxides: Molybdenum Trioxide Species as the Origin of Allylic Byproducts

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