Registration Number
0214U000491,
0113U002858
, R & D reports
Title
Homo- and heterometallic intermediates and products of 3d metals mono- and binuclear pyrazolate complexes intraction with the corresponding carboxylates, as catalysts (models of catalysts) of hydroperoxides formation and transformations.
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Head
Kamalov G.L.,
Registration Date
12-03-2014
Organization
A.V.Bogatsky Physico-Chemical Institute of the National Academy of Sciences of Ukraine
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Monohydroperoxide (НР), benzaldehyde (BAld) and benzoic acid (BAc) are basic products of dibenzyl ether (DBE) oxidation in the presence of cobalt(II), copper(II) and nickel(II) homo- and heteroleptic carboxlate and carboxylate-pyrazolate complexes (24 compounds). DBE oxidation is characterized by high rate and BАld selectivity in the presence of Co(II) complexes, whereas in the case of Cu(II) complexes, HP prevails in the oxidate. The Cu(II) complexes carry out deeper DBE oxidation to BAc in comparison with Co(II) complexes. For catalytic activity of Cu(II) binuclear complexes with the "chinese lantern" structure, such row of "influence" of terminal ligands is educed: Hdmpz > NEt3 ? PСу3 ? MeOH > PPh3 ? OPPh3 ? OC(NH2). At cyclohexene (СН) oxidation in the presence of pivalate complexes with CoM2O framework (M = Co - I, Cr - II, Fe - III) and NiCr2OPiv6·3Ppy (IV), CH conversion and initial rates of hydroperoxide accumulation are comparable with such for DBE, and selectivity changes thus: IV<I<II<<III. In the presence of complexes I and II, there is practically synchronous formation of CHon and CHol on the same catalytic centers. Formation of "peroxo-dimers" М-О-О-М/ is possible in the presence of pivalates II-IV. Reactivity of О-О bonds will be different, as a result CH oxidation rate and selectivity will change.
Product Description
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Іванов Ю.Е.
Камалов Г.Л.
Коцеруба В.А.
Левченко О.О.
Чіхічін Д.Г.
Яволовський А.О.
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2020-04-02
