Commercial gold(III)complex supported on functionalized carbon materials as catalyst for cyclohexane hydrocarboxylation

Ekaterina Pakrieva, Ana P.C. Ribeiro, Luísa M.D.R.S. Martins, Inês A.S. Matias, Sónia A.C. Carabineiro, Ekaterina Kolobova, Armando J.L. Pombeiro, José L. Figueiredo, Alexey Pestryakov

Research output: Contribution to journalArticle

Abstract

The commercial dichloro(2-pyridinecarboxylato)gold(III)complex (1), anchored on different carbon materials, is reported for the first time as a catalyst in the cyclohexane hydrocarboxylation to cyclohexanecarboxylic acid. The reaction was carried out in the presence of CO and water, peroxodisulfate, at ca. 50 °C, with 1 in solution and anchored on carbon nanotubes, carbon xerogel or activated carbon, with three different surface chemistries: original forms (CNT, CX or AC, respectively), oxidized with HNO3 (-ox)or oxidized with HNO3 and subsequently treated with NaOH (-ox-Na). 1@CNT-ox-Na was the best catalyst, yielding up to 78% of cyclohexanecarboxylic with a selectivity of 99%. Recycling studies showed that the catalyst was stable up to 4 cycles, the first decrease (11%)on the hydrocarboxylation yield being observed on the 5th cycle. No leaching of gold was found into the solution. The hydrocarboxylation of other cycloalkanes (cyclopentane, cycloheptane and cyclooctane)was also tested in the best conditions found for cyclohexane, but the respective carboxylic acids were obtained in considerably lower yields, which can be explained by different stabilities of cycloalkyl radicals.

Original languageEnglish
JournalCatalysis Today
DOIs
Publication statusPublished - 1 Jan 2019

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Cyclohexane
Gold
Carbon
Catalysts
Cycloheptanes
Cycloparaffins
Cyclopentanes
Xerogels
Carbon Nanotubes
Carbon Monoxide
Carboxylic Acids
Surface chemistry
Carboxylic acids
Activated carbon
Leaching
Recycling
Carbon nanotubes
Acids
Water

Keywords

  • Carbon materials functionalization
  • Cyclohexane hydrocarboxylation
  • Cyclohexanecarboxylic acid
  • C̶[sbnd]H activation
  • Dichloro(2-pyridinecarboxylato)gold(III)complex

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

Cite this

Commercial gold(III)complex supported on functionalized carbon materials as catalyst for cyclohexane hydrocarboxylation. / Pakrieva, Ekaterina; Ribeiro, Ana P.C.; Martins, Luísa M.D.R.S.; Matias, Inês A.S.; Carabineiro, Sónia A.C.; Kolobova, Ekaterina; Pombeiro, Armando J.L.; Figueiredo, José L.; Pestryakov, Alexey.

In: Catalysis Today, 01.01.2019.

Research output: Contribution to journalArticle

Pakrieva, Ekaterina ; Ribeiro, Ana P.C. ; Martins, Luísa M.D.R.S. ; Matias, Inês A.S. ; Carabineiro, Sónia A.C. ; Kolobova, Ekaterina ; Pombeiro, Armando J.L. ; Figueiredo, José L. ; Pestryakov, Alexey. / Commercial gold(III)complex supported on functionalized carbon materials as catalyst for cyclohexane hydrocarboxylation. In: Catalysis Today. 2019.
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AU - Matias, Inês A.S.

AU - Carabineiro, Sónia A.C.

AU - Kolobova, Ekaterina

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AB - The commercial dichloro(2-pyridinecarboxylato)gold(III)complex (1), anchored on different carbon materials, is reported for the first time as a catalyst in the cyclohexane hydrocarboxylation to cyclohexanecarboxylic acid. The reaction was carried out in the presence of CO and water, peroxodisulfate, at ca. 50 °C, with 1 in solution and anchored on carbon nanotubes, carbon xerogel or activated carbon, with three different surface chemistries: original forms (CNT, CX or AC, respectively), oxidized with HNO3 (-ox)or oxidized with HNO3 and subsequently treated with NaOH (-ox-Na). 1@CNT-ox-Na was the best catalyst, yielding up to 78% of cyclohexanecarboxylic with a selectivity of 99%. Recycling studies showed that the catalyst was stable up to 4 cycles, the first decrease (11%)on the hydrocarboxylation yield being observed on the 5th cycle. No leaching of gold was found into the solution. The hydrocarboxylation of other cycloalkanes (cyclopentane, cycloheptane and cyclooctane)was also tested in the best conditions found for cyclohexane, but the respective carboxylic acids were obtained in considerably lower yields, which can be explained by different stabilities of cycloalkyl radicals.

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