Registration Number
0213U007453,
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
14-11-2013
Organization
A.V.Bogatsky Physico-Chemical Institute of the National Academy of Sciences of Ukraine
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Kinetics of the cyclohexene hydroperoxide decomposition at the presence of homo- and heteroligands pivalate complexes of cobalt with nuclearity 1-4: [CoPiv2]n, n = 1,2; [Co2(Piv)2L2(Hdmpz)4](otf)2(thf)n, L = OH2, MeCN, n = 1,2; Co4LnPiv6(ROH)6, R=Et, Pr, L=OH, OMe, n=2,4) is investigated. The row of catalytic activity depending on nuclearity is determined: Со1<Со2 <Со3 <Со4. Reaction is described by the equation of the second order, the reaction order on the catalyst makes from 0,4 to 0,9. In the presence of complexes CoL2(Hdmpz)2 (L = OOCPh, (CF3)2pz); Con(dmpz)m(Hdmpz)2L2 (L = Piv, OAc, n = 2,3, m = 2,4); Cun(Piv)n(Hdmpz)mL, (L = MeCN, (MeOH)2); (Piv)Cu((CF3)2pz)2(Piv)Cu(PivH·NEt3) and Cu3(ОH)(pz)3(Piv)(PivOH·NEt3)(Hpz)(PivH) in the mixed solvent (DBE:dioxane), dependence of H2O2 decomposition rate on DBE concentration passes through a maximum. Complexes Cu are less active, than Co. At volume ratio DBE:dioxane = 1:1, the binuclear complex Co(II) shows the greater catalytic activity compared with trinuclear complex and pyrazolate complex Co((CF3)2pz)2(Hdmpz)2 is more active, than benzoate complex Co(OOCPh)2(Hdmpz)2. The binuclear complex Co(II) shows the greater catalytic activity in Н2О2 decomposition in dioxane and its mixes with DBE, whereas corresponding trinuclear complex is more active in the mixed solvents (dioxane: cyclohexene, cylohexane). It is established, that the basic product of DBE oxidation with the complex (СоII)3(OOCBut)6(NEt3)2 in a solution CH2Cl2-benzene (4:1) is hexanuclear complex [(CoIII)6(?4-O)2(?3-O)2(?-OOCBut)9(OH)2(HOOCBut)](HNEt3)·0.5DBE·0.5C6H6,
Product Description
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Камалов Г.Л.
Коцеруба В.А.
Левченко О.О
Чіхічін Д.Г.
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2020-04-02
