Structural features and catalytic reactivity of [Pd{(Ph2P)2N(CH2)3Si(OCH3)3-κP,P′}I2] and related complexes in hydroalkoxycarbonylation and Suzuki–Miyaura C−C cross-coupling reactions

Ioannis K. Stamatopoulos, Maria Kapsi, Maria Roulia, Georgios C. Vougioukalakis, Catherine P. Raptopoulou, Vassilis Psycharis, Ioannis D. Kostas, L. Kollár, Panayotis Kyritsis

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Abstract

The synthesis, as well as the structural and spectroscopic characterization of the palladium(II) complex [Pd{(Ph2P)2N(CH2)3Si(OCH3)3-κP,P′}I2], bearing the bis(phosphino)amine ligand (P,P) = (Ph2P)2N(CH2)3Si(OCH3)3, is described. X-ray crystallography studies revealed a square planar PdP2I2 coordination sphere, the structural features of which are compared with those of analogous nickel(II), palladium(II) and platinum(II) complexes. The three complexes [Pd(P,P)X2], X = Cl, Br, I, along with [Pd{(Ph2P)2N((S)-CHPhMe)-κP,P′}Cl2] and [Pd{(Ph2PSe)(Ph2P)N((S)-CHMePh)-κP,Se}Cl2], were tested as catalysts in homogeneous hydroalkoxycarbonylation reactions. The hydroalkoxycarbonylation of styrene proved to be perfectly regioselective towards the branched ester. Complex [Pd(P,P)Cl2] showed remarkably higher activity compared with that of [Pd(P,P)X2], X = Br, I. Furthermore, complex [Pd(P,P)I2] was studied as a homogeneous catalyst precursor in the Suzuki–Miyaura C−C coupling reaction between aryl bromides and phenylboronic acid. Complex [Pd(P,P)I2] was immobilized onto STx–1 montmorillonite clay and the catalytic reactivity of the heterogenized catalyst was also investigated in both hydroalkoxycarbonylation and Suzuki–Miyaura reactions.

Original languageEnglish
Pages (from-to)292-298
Number of pages7
JournalPolyhedron
Volume151
DOIs
Publication statusPublished - Sep 1 2018

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cross coupling
reactivity
Palladium
catalysts
Catalysts
palladium
Bearings (structural)
Bentonite
Styrene
X ray crystallography
montmorillonite
Clay minerals
Platinum
Nickel
Bromides
styrenes
clays
crystallography
Amines
bromides

Keywords

  • Bis(phosphino)amine ligand
  • Carbonylation reaction
  • Palladium
  • Suzuki–Miyaura cross-coupling
  • X-ray crystallography

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

Cite this

Structural features and catalytic reactivity of [Pd{(Ph2P)2N(CH2)3Si(OCH3)3-κP,P′}I2] and related complexes in hydroalkoxycarbonylation and Suzuki–Miyaura C−C cross-coupling reactions. / Stamatopoulos, Ioannis K.; Kapsi, Maria; Roulia, Maria; Vougioukalakis, Georgios C.; Raptopoulou, Catherine P.; Psycharis, Vassilis; Kostas, Ioannis D.; Kollár, L.; Kyritsis, Panayotis.

In: Polyhedron, Vol. 151, 01.09.2018, p. 292-298.

Research output: Contribution to journalArticle

Stamatopoulos, Ioannis K. ; Kapsi, Maria ; Roulia, Maria ; Vougioukalakis, Georgios C. ; Raptopoulou, Catherine P. ; Psycharis, Vassilis ; Kostas, Ioannis D. ; Kollár, L. ; Kyritsis, Panayotis. / Structural features and catalytic reactivity of [Pd{(Ph2P)2N(CH2)3Si(OCH3)3-κP,P′}I2] and related complexes in hydroalkoxycarbonylation and Suzuki–Miyaura C−C cross-coupling reactions. In: Polyhedron. 2018 ; Vol. 151. pp. 292-298.
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abstract = "The synthesis, as well as the structural and spectroscopic characterization of the palladium(II) complex [Pd{(Ph2P)2N(CH2)3Si(OCH3)3-κP,P′}I2], bearing the bis(phosphino)amine ligand (P,P) = (Ph2P)2N(CH2)3Si(OCH3)3, is described. X-ray crystallography studies revealed a square planar PdP2I2 coordination sphere, the structural features of which are compared with those of analogous nickel(II), palladium(II) and platinum(II) complexes. The three complexes [Pd(P,P)X2], X = Cl, Br, I, along with [Pd{(Ph2P)2N((S)-CHPhMe)-κP,P′}Cl2] and [Pd{(Ph2PSe)(Ph2P)N((S)-CHMePh)-κP,Se}Cl2], were tested as catalysts in homogeneous hydroalkoxycarbonylation reactions. The hydroalkoxycarbonylation of styrene proved to be perfectly regioselective towards the branched ester. Complex [Pd(P,P)Cl2] showed remarkably higher activity compared with that of [Pd(P,P)X2], X = Br, I. Furthermore, complex [Pd(P,P)I2] was studied as a homogeneous catalyst precursor in the Suzuki–Miyaura C−C coupling reaction between aryl bromides and phenylboronic acid. Complex [Pd(P,P)I2] was immobilized onto STx–1 montmorillonite clay and the catalytic reactivity of the heterogenized catalyst was also investigated in both hydroalkoxycarbonylation and Suzuki–Miyaura reactions.",
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T1 - Structural features and catalytic reactivity of [Pd{(Ph2P)2N(CH2)3Si(OCH3)3-κP,P′}I2] and related complexes in hydroalkoxycarbonylation and Suzuki–Miyaura C−C cross-coupling reactions

AU - Stamatopoulos, Ioannis K.

AU - Kapsi, Maria

AU - Roulia, Maria

AU - Vougioukalakis, Georgios C.

AU - Raptopoulou, Catherine P.

AU - Psycharis, Vassilis

AU - Kostas, Ioannis D.

AU - Kollár, L.

AU - Kyritsis, Panayotis

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N2 - The synthesis, as well as the structural and spectroscopic characterization of the palladium(II) complex [Pd{(Ph2P)2N(CH2)3Si(OCH3)3-κP,P′}I2], bearing the bis(phosphino)amine ligand (P,P) = (Ph2P)2N(CH2)3Si(OCH3)3, is described. X-ray crystallography studies revealed a square planar PdP2I2 coordination sphere, the structural features of which are compared with those of analogous nickel(II), palladium(II) and platinum(II) complexes. The three complexes [Pd(P,P)X2], X = Cl, Br, I, along with [Pd{(Ph2P)2N((S)-CHPhMe)-κP,P′}Cl2] and [Pd{(Ph2PSe)(Ph2P)N((S)-CHMePh)-κP,Se}Cl2], were tested as catalysts in homogeneous hydroalkoxycarbonylation reactions. The hydroalkoxycarbonylation of styrene proved to be perfectly regioselective towards the branched ester. Complex [Pd(P,P)Cl2] showed remarkably higher activity compared with that of [Pd(P,P)X2], X = Br, I. Furthermore, complex [Pd(P,P)I2] was studied as a homogeneous catalyst precursor in the Suzuki–Miyaura C−C coupling reaction between aryl bromides and phenylboronic acid. Complex [Pd(P,P)I2] was immobilized onto STx–1 montmorillonite clay and the catalytic reactivity of the heterogenized catalyst was also investigated in both hydroalkoxycarbonylation and Suzuki–Miyaura reactions.

AB - The synthesis, as well as the structural and spectroscopic characterization of the palladium(II) complex [Pd{(Ph2P)2N(CH2)3Si(OCH3)3-κP,P′}I2], bearing the bis(phosphino)amine ligand (P,P) = (Ph2P)2N(CH2)3Si(OCH3)3, is described. X-ray crystallography studies revealed a square planar PdP2I2 coordination sphere, the structural features of which are compared with those of analogous nickel(II), palladium(II) and platinum(II) complexes. The three complexes [Pd(P,P)X2], X = Cl, Br, I, along with [Pd{(Ph2P)2N((S)-CHPhMe)-κP,P′}Cl2] and [Pd{(Ph2PSe)(Ph2P)N((S)-CHMePh)-κP,Se}Cl2], were tested as catalysts in homogeneous hydroalkoxycarbonylation reactions. The hydroalkoxycarbonylation of styrene proved to be perfectly regioselective towards the branched ester. Complex [Pd(P,P)Cl2] showed remarkably higher activity compared with that of [Pd(P,P)X2], X = Br, I. Furthermore, complex [Pd(P,P)I2] was studied as a homogeneous catalyst precursor in the Suzuki–Miyaura C−C coupling reaction between aryl bromides and phenylboronic acid. Complex [Pd(P,P)I2] was immobilized onto STx–1 montmorillonite clay and the catalytic reactivity of the heterogenized catalyst was also investigated in both hydroalkoxycarbonylation and Suzuki–Miyaura reactions.

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KW - Carbonylation reaction

KW - Palladium

KW - Suzuki–Miyaura cross-coupling

KW - X-ray crystallography

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