Результаты исследований: Научные публикации в периодических изданиях › статья › Рецензирование
Benzaldoxime to benzamide rearrangement catalysed by rhodium(III) hydroxocomplexes : The influence of polynuclear species. / Berdyugin, Semen; Volchek, Victoria; Asanova, Tatyana и др.
в: Applied Catalysis A: General, Том 587, 117242, 25.10.2019.Результаты исследований: Научные публикации в периодических изданиях › статья › Рецензирование
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TY - JOUR
T1 - Benzaldoxime to benzamide rearrangement catalysed by rhodium(III) hydroxocomplexes
T2 - The influence of polynuclear species
AU - Berdyugin, Semen
AU - Volchek, Victoria
AU - Asanova, Tatyana
AU - Kolesov, Boris
AU - Gerasimov, Evgeny
AU - Filatov, Evgeny
AU - Vasilchenko, Danila
AU - Korenev, Sergey
N1 - Publisher Copyright: © 2019 Elsevier B.V. Copyright: Copyright 2020 Elsevier B.V., All rights reserved. Publisher Copyright: © 2019 Elsevier B.V.
PY - 2019/10/25
Y1 - 2019/10/25
N2 - Rhodium(III) hydroxide was shown previously to possess the catalytic activity in the rearrangement reaction of primary oximes to amides. Alkaline solutions of rhodium(III) chlorocomplexes are routinely used for Rh(OH)3 preparation and allow for a diversity of rhodium hydroxocomplexes that hold a wide range of catalytic properties. In this study, two Al2O3 supported catalysts containing 1) exclusively [Rh(OH)6]3− species and 2) a mixture of rhodium hydroxocomplexes with one to four rhodium atoms ([Rh(OH)6]3–, [Rh2(μ−OH)2(OH)8]4–, [Rh3(μ−OH)3(OH)12]6–, [Rh4(μ−OH)6(OH)12]6) were prepared, characterised (XRD, Raman, EXAFS) and tested in the benzaldoxime to benzamide rearrangement. The catalyst containing polynuclear complexes possessed at least three times higher turnover frequency (TOF) and better selectivity than the [Rh(OH)6]3– based catalyst. According to the EXAFS data, the reduction of rhodium(III) took place under reaction conditions yielding small rhodium clusters (CNRh-Rh = 4), which were proposed to be the active sites of catalysts.
AB - Rhodium(III) hydroxide was shown previously to possess the catalytic activity in the rearrangement reaction of primary oximes to amides. Alkaline solutions of rhodium(III) chlorocomplexes are routinely used for Rh(OH)3 preparation and allow for a diversity of rhodium hydroxocomplexes that hold a wide range of catalytic properties. In this study, two Al2O3 supported catalysts containing 1) exclusively [Rh(OH)6]3− species and 2) a mixture of rhodium hydroxocomplexes with one to four rhodium atoms ([Rh(OH)6]3–, [Rh2(μ−OH)2(OH)8]4–, [Rh3(μ−OH)3(OH)12]6–, [Rh4(μ−OH)6(OH)12]6) were prepared, characterised (XRD, Raman, EXAFS) and tested in the benzaldoxime to benzamide rearrangement. The catalyst containing polynuclear complexes possessed at least three times higher turnover frequency (TOF) and better selectivity than the [Rh(OH)6]3– based catalyst. According to the EXAFS data, the reduction of rhodium(III) took place under reaction conditions yielding small rhodium clusters (CNRh-Rh = 4), which were proposed to be the active sites of catalysts.
KW - Heterogeneous catalysts
KW - Primary amides
KW - rhodium(III) hydroxocomplexes
KW - MILD
KW - ONE-POT SYNTHESIS
KW - ACIDS
KW - PRIMARY AMIDES
KW - NANOPARTICLE
KW - ALDOXIMES
KW - HYDRATION
KW - EXAFS
KW - WATER
UR - http://www.scopus.com/inward/record.url?scp=85072201658&partnerID=8YFLogxK
U2 - 10.1016/j.apcata.2019.117242
DO - 10.1016/j.apcata.2019.117242
M3 - Article
AN - SCOPUS:85072201658
VL - 587
JO - Applied Catalysis A: General
JF - Applied Catalysis A: General
SN - 0926-860X
M1 - 117242
ER -
ID: 21538388