Kinetics and Mechanism of the Homogeneous oxidation of n-Butenes to Methyl Ethyl Ketone in a Solution of Mo-V-Phosphoric Heteropoly Acid in the Presence of Palladium Pyridine-2,6-Dicarboxylate Full article
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Kinetics and Catalysis
ISSN: 0023-1584 , E-ISSN: 1608-3210 |
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| Output data | Year: 2011, Volume: 52, Number: 6, Pages: 828-834 Pages count : 7 DOI: 10.1134/S0023158411060164 | ||
| Tags | Dioxygen; Methyl Ethyl Ketone; Heteropoly Acid; Tridentate Ligand; Dipicolinic Acid | ||
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Abstract:
In catalytic two-step n-butene oxidation with dioxygen to methyl ethyl ketone, the first step is the oxidation of n-C4H8 with an aqueous solution of Mo-V-P heteropoly acid in the presence of Pd(II) complexes. The kinetics of n-butene oxidation with solutions of H7PV4Mo8O40 (HPA-4) in the presence of the Pd(II) dipicolinate complex (H2O)PdII(dipic) (I), where dipic2− is the tridentate ligand 2,6-NC5H3(COO−)2, is studied. Calculation shows that, at the ratio dipic2−: Pd(II) = 1: 1, the ligand decreases the redox potential of the Pd(II)/Pdmet system from 0.92 to 0.73–0.77, due to which Pd(II) is stabilized in reduced solutions of HPA-4. The reaction is first-order with respect to n-C4H8. Its order with respect to Pd(II) is slightly below unity, and its order with respect to HPA-4 is relatively low (∼0.63). The activation energy of but-1-ene oxidation in the temperature range from 40 to 80°C is 49.0 kJ/mol, and that of the oxidation of but-2-ene is 55.6 kJ/mol. The mechanism of the reaction involving the cis-diaqua complex [(H2O)2PdII(Hdipic)]+, which forms reversibly from complex I, is proposed. The reaction rate is shown to increase with an increase in the HPA-4 concentration due to an increase in the acidity of the solution.
Cite:
Odyakov V.F.
, Zhizhina E.G.
Kinetics and Mechanism of the Homogeneous oxidation of n-Butenes to Methyl Ethyl Ketone in a Solution of Mo-V-Phosphoric Heteropoly Acid in the Presence of Palladium Pyridine-2,6-Dicarboxylate
Kinetics and Catalysis. 2011. V.52. N6. P.828-834. DOI: 10.1134/S0023158411060164 WOS Scopus РИНЦ ANCAN OpenAlex
Kinetics and Mechanism of the Homogeneous oxidation of n-Butenes to Methyl Ethyl Ketone in a Solution of Mo-V-Phosphoric Heteropoly Acid in the Presence of Palladium Pyridine-2,6-Dicarboxylate
Kinetics and Catalysis. 2011. V.52. N6. P.828-834. DOI: 10.1134/S0023158411060164 WOS Scopus РИНЦ ANCAN OpenAlex
Original:
Одяков В.Ф.
, Жижина Е.Г.
Кинетика и механизм гомогенного окисления н-бутенов в метилэтилкетон в растворе Mo-V-фосфорной гетерополикислоты в присутствии пиридин-2,6-дикарбоксилата палладия
Кинетика и катализ. 2011. Т.52. №6. С.849-855. РИНЦ
Кинетика и механизм гомогенного окисления н-бутенов в метилэтилкетон в растворе Mo-V-фосфорной гетерополикислоты в присутствии пиридин-2,6-дикарбоксилата палладия
Кинетика и катализ. 2011. Т.52. №6. С.849-855. РИНЦ
Dates:
| Submitted: | Feb 25, 2011 |
| Published online: | Nov 30, 2011 |
| Published print: | Dec 1, 2011 |
Identifiers:
| Web of science: | WOS:000297630200009 |
| Scopus: | 2-s2.0-84855892372 |
| Elibrary: | 18033729 |
| Chemical Abstracts: | 2011:1539240 |
| Chemical Abstracts (print): | 156:257165 |
| OpenAlex: | W2054956821 |