SBA-15/POSS-Imidazolium Hybrid as Catalytic Nanoreactor: the role of the Support in the Stabilization of Palladium Species for C−C Cross Coupling Reactions.

Carla Calabrese, Vincenzo Campisciano, Fabiana Siragusa, Leonarda F. Liotta, Carmela Aprile, Michelangelo Gruttadauria, Francesco Giacalone

Research output: Contribution to journalArticle

Abstract

Supported imidazolium modified polyhedral oligomeric silsesquioxanes (POSS) on SBA-15 have been used as platform for Pd(II) species. The so-obtained material was firstly characterized by means of TGA, solid state NMR, TEM, XPS, SAXS, porosimetry and ICP-OES and it was successfully tested as pre-catalyst in C−C cross couplings, namely Suzuki-Miyaura and Heck reactions. In both cases, the solid proved to be highly efficient and easily recoverable from the reaction mixture. The recyclability was verified for up to seven cycles without showing any activity decrease. Interestingly, only Pd(II) was detected in the reused catalyst in the Heck reaction. Therefore, the versatility of the material was investigated by using various aryl halides. Our palladium nanocomposite was able to promote both Suzuki and Heck reactions down to 0.0007 mol% showing outstanding turnover frequency (TOF) values of 114,286 and 32,381 h −1 , respectively. Comparison with the palladium catalyst on SiO 2 -POSS-imidazolium support showed interesting differences in terms of stabilization of Pd species and recyclability. The excellent outcome of the reactions could be ascribed to the textural properties of the SBA-15 support and the presence of the imidazolium-POSS nanocage within the pores of SBA-15, that worked as a sort of nanoreactor. (Figure presented.).

Original languageEnglish
Pages (from-to)3758-3767
Number of pages10
JournalAdvanced Synthesis and Catalysis
Volume361
Issue number16
DOIs
Publication statusPublished - 1 Jan 2019

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Nanoreactors
Palladium
Stabilization
Catalysts
Catalyst supports
Nanocomposites
X ray photoelectron spectroscopy
Nuclear magnetic resonance
Transmission electron microscopy
SBA-15

Keywords

  • C−C coupling
  • Heck reaction
  • heterogeneous catalysis
  • palladium
  • Suzuki-Miyaura reaction

Cite this

@article{2190fec0a2da4b0cb1566e252a9be9bc,
title = "SBA-15/POSS-Imidazolium Hybrid as Catalytic Nanoreactor: the role of the Support in the Stabilization of Palladium Species for C−C Cross Coupling Reactions.",
abstract = "Supported imidazolium modified polyhedral oligomeric silsesquioxanes (POSS) on SBA-15 have been used as platform for Pd(II) species. The so-obtained material was firstly characterized by means of TGA, solid state NMR, TEM, XPS, SAXS, porosimetry and ICP-OES and it was successfully tested as pre-catalyst in C−C cross couplings, namely Suzuki-Miyaura and Heck reactions. In both cases, the solid proved to be highly efficient and easily recoverable from the reaction mixture. The recyclability was verified for up to seven cycles without showing any activity decrease. Interestingly, only Pd(II) was detected in the reused catalyst in the Heck reaction. Therefore, the versatility of the material was investigated by using various aryl halides. Our palladium nanocomposite was able to promote both Suzuki and Heck reactions down to 0.0007 mol{\%} showing outstanding turnover frequency (TOF) values of 114,286 and 32,381 h −1 , respectively. Comparison with the palladium catalyst on SiO 2 -POSS-imidazolium support showed interesting differences in terms of stabilization of Pd species and recyclability. The excellent outcome of the reactions could be ascribed to the textural properties of the SBA-15 support and the presence of the imidazolium-POSS nanocage within the pores of SBA-15, that worked as a sort of nanoreactor. (Figure presented.).",
keywords = "C−C coupling, Heck reaction, heterogeneous catalysis, palladium, Suzuki-Miyaura reaction",
author = "Carla Calabrese and Vincenzo Campisciano and Fabiana Siragusa and Liotta, {Leonarda F.} and Carmela Aprile and Michelangelo Gruttadauria and Francesco Giacalone",
year = "2019",
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language = "English",
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TY - JOUR

T1 - SBA-15/POSS-Imidazolium Hybrid as Catalytic Nanoreactor

T2 - the role of the Support in the Stabilization of Palladium Species for C−C Cross Coupling Reactions.

AU - Calabrese, Carla

AU - Campisciano, Vincenzo

AU - Siragusa, Fabiana

AU - Liotta, Leonarda F.

AU - Aprile, Carmela

AU - Gruttadauria, Michelangelo

AU - Giacalone, Francesco

PY - 2019/1/1

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N2 - Supported imidazolium modified polyhedral oligomeric silsesquioxanes (POSS) on SBA-15 have been used as platform for Pd(II) species. The so-obtained material was firstly characterized by means of TGA, solid state NMR, TEM, XPS, SAXS, porosimetry and ICP-OES and it was successfully tested as pre-catalyst in C−C cross couplings, namely Suzuki-Miyaura and Heck reactions. In both cases, the solid proved to be highly efficient and easily recoverable from the reaction mixture. The recyclability was verified for up to seven cycles without showing any activity decrease. Interestingly, only Pd(II) was detected in the reused catalyst in the Heck reaction. Therefore, the versatility of the material was investigated by using various aryl halides. Our palladium nanocomposite was able to promote both Suzuki and Heck reactions down to 0.0007 mol% showing outstanding turnover frequency (TOF) values of 114,286 and 32,381 h −1 , respectively. Comparison with the palladium catalyst on SiO 2 -POSS-imidazolium support showed interesting differences in terms of stabilization of Pd species and recyclability. The excellent outcome of the reactions could be ascribed to the textural properties of the SBA-15 support and the presence of the imidazolium-POSS nanocage within the pores of SBA-15, that worked as a sort of nanoreactor. (Figure presented.).

AB - Supported imidazolium modified polyhedral oligomeric silsesquioxanes (POSS) on SBA-15 have been used as platform for Pd(II) species. The so-obtained material was firstly characterized by means of TGA, solid state NMR, TEM, XPS, SAXS, porosimetry and ICP-OES and it was successfully tested as pre-catalyst in C−C cross couplings, namely Suzuki-Miyaura and Heck reactions. In both cases, the solid proved to be highly efficient and easily recoverable from the reaction mixture. The recyclability was verified for up to seven cycles without showing any activity decrease. Interestingly, only Pd(II) was detected in the reused catalyst in the Heck reaction. Therefore, the versatility of the material was investigated by using various aryl halides. Our palladium nanocomposite was able to promote both Suzuki and Heck reactions down to 0.0007 mol% showing outstanding turnover frequency (TOF) values of 114,286 and 32,381 h −1 , respectively. Comparison with the palladium catalyst on SiO 2 -POSS-imidazolium support showed interesting differences in terms of stabilization of Pd species and recyclability. The excellent outcome of the reactions could be ascribed to the textural properties of the SBA-15 support and the presence of the imidazolium-POSS nanocage within the pores of SBA-15, that worked as a sort of nanoreactor. (Figure presented.).

KW - C−C coupling

KW - Heck reaction

KW - heterogeneous catalysis

KW - palladium

KW - Suzuki-Miyaura reaction

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