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Immobilization of [Pd{(Ph2P)2N(CH2)3Si(OCH3)3-κP,P'}X2] (X=Cl, Br) onto Montmorillonite: Investigating their Performance as Homogeneous or Heterogenized Suzuki-Miyaura Catalysts

Immobilization of [Pd{(Ph2P)2N(CH2)3Si(OCH3)3-κP,P'}X2] (X=Cl, Br) onto Montmorillonite: Investigating their Performance as Homogeneous or Heterogenized Suzuki-Miyaura Catalysts
Immobilization of [Pd{(Ph2P)2N(CH2)3Si(OCH3)3-κP,P'}X2] (X=Cl, Br) onto Montmorillonite: Investigating their Performance as Homogeneous or Heterogenized Suzuki-Miyaura Catalysts
Two palladium complexes, [Pd{(Ph2P)2N(CH2)3Si(OCH3)3-κP,P'}X2], X=Cl (2), Br (3), were synthesized and characterized by spectroscopic methods and X-ray crystallography. Complexes 2 and 3 contain a PdP2X2 square planar coordination sphere exhibiting small endocyclic P–Pd–P angles [71.49(4) and 71.53(5)°, respectively], the magnitude of which is controlled by the formation of the Pd–P–N–P four-membered chelating ring. Complexes 2 and 3 were found to be efficient catalysts in the Suzuki-Miyaura cross-coupling reaction of aryl bromides with phenylboronic acid at ambient or elevated temperature. At 100 °C, using 0.1 mol% of palladium loading, high conversions were observed even after 15 min. Both complexes were immobilized onto STx-1 montmorillonite clay via their −Si(OMe)3 moiety, a process investigated by X-ray powder diffraction, X-ray fluorescence spectrometry, solid-state 31P NMR spectroscopy and Scanning Electron Microscopy. The immobilized complexes, as heterogenized catalysts, displayed higher activity in the Suzuki-Miyaura coupling compared to that of the free complexes. The recyclability of the former was also explored.
crystal structure, immobilized complex, palladium complex, PNP Ligand, STx–1 montmorillonite, Suzuki-Miyaura cross-coupling
12051-12059
Stamatopoulos, Ioannis
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Roulia, Maria
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Vallianatou, Kalliopi A.
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Raptopoulou, Catherine P.
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Psycharis, Vassilis
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Carravetta, Marina
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Papachristodoulou, Christina
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Hey-Hawkins, Evamarie
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Kostas, Ioannis D.
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Kyritsis, Panayotis
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Stamatopoulos, Ioannis
625597e9-c960-4819-a90c-ccda7273d5ca
Roulia, Maria
eae6ce4b-554e-42e0-be1c-7832d1e5109b
Vallianatou, Kalliopi A.
976d162b-ce61-4587-b75d-ac822591b36e
Raptopoulou, Catherine P.
9bd1f70c-2922-4e14-a86b-5a23174f5b97
Psycharis, Vassilis
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Carravetta, Marina
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Papachristodoulou, Christina
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Hey-Hawkins, Evamarie
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Kostas, Ioannis D.
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Kyritsis, Panayotis
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Stamatopoulos, Ioannis, Roulia, Maria, Vallianatou, Kalliopi A., Raptopoulou, Catherine P., Psycharis, Vassilis, Carravetta, Marina, Papachristodoulou, Christina, Hey-Hawkins, Evamarie, Kostas, Ioannis D. and Kyritsis, Panayotis (2017) Immobilization of [Pd{(Ph2P)2N(CH2)3Si(OCH3)3-κP,P'}X2] (X=Cl, Br) onto Montmorillonite: Investigating their Performance as Homogeneous or Heterogenized Suzuki-Miyaura Catalysts. ChemistrySelect, 2 (36), 12051-12059. (doi:10.1002/slct.201702601).

Record type: Article

Abstract

Two palladium complexes, [Pd{(Ph2P)2N(CH2)3Si(OCH3)3-κP,P'}X2], X=Cl (2), Br (3), were synthesized and characterized by spectroscopic methods and X-ray crystallography. Complexes 2 and 3 contain a PdP2X2 square planar coordination sphere exhibiting small endocyclic P–Pd–P angles [71.49(4) and 71.53(5)°, respectively], the magnitude of which is controlled by the formation of the Pd–P–N–P four-membered chelating ring. Complexes 2 and 3 were found to be efficient catalysts in the Suzuki-Miyaura cross-coupling reaction of aryl bromides with phenylboronic acid at ambient or elevated temperature. At 100 °C, using 0.1 mol% of palladium loading, high conversions were observed even after 15 min. Both complexes were immobilized onto STx-1 montmorillonite clay via their −Si(OMe)3 moiety, a process investigated by X-ray powder diffraction, X-ray fluorescence spectrometry, solid-state 31P NMR spectroscopy and Scanning Electron Microscopy. The immobilized complexes, as heterogenized catalysts, displayed higher activity in the Suzuki-Miyaura coupling compared to that of the free complexes. The recyclability of the former was also explored.

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Supporting information for Immobilization of the complexes [Pd{(Ph2P)2N(CH2)3Si(OCH3)3-κP,P´}X2] (X = Cl, Br) onto STx–1 montmorillonite: An investigation of their performance as homogeneous or heterogenized Suzuki-Miyaura catalysts
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Accepted/In Press date: 18 December 2017
e-pub ahead of print date: 21 December 2017
Keywords: crystal structure, immobilized complex, palladium complex, PNP Ligand, STx–1 montmorillonite, Suzuki-Miyaura cross-coupling

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Local EPrints ID: 417308
URI: http://eprints.soton.ac.uk/id/eprint/417308
PURE UUID: 198f50ca-0d72-446d-ba36-7ddc9f03f58b
ORCID for Marina Carravetta: ORCID iD orcid.org/0000-0002-6296-2104

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Date deposited: 29 Jan 2018 17:30
Last modified: 16 Mar 2024 06:08

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Contributors

Author: Ioannis Stamatopoulos
Author: Maria Roulia
Author: Kalliopi A. Vallianatou
Author: Catherine P. Raptopoulou
Author: Vassilis Psycharis
Author: Christina Papachristodoulou
Author: Evamarie Hey-Hawkins
Author: Ioannis D. Kostas
Author: Panayotis Kyritsis

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