A mixed phosphine−iminophosphorane tetradentate ligand: Synthesis, coordination to group 10 metal centers, and use as catalyst in Suzuki−Miyaura coupling

Antoine Buchard, Bruno Komly, Audrey Auffrant, Xavier F. Le Goff, Pascal Le Floch

Research output: Contribution to journalArticle

22 Citations (Scopus)

Abstract

The novel tetradentate ligand 1, associating two phosphines and two iminophosphorane moieties, was easily synthesized from commercially available bis(diphenylphosphino)methane and ethylenediamine via the preparation of the bis(phosphine−aminophosphonium) adduct 1-(HBr)2. Deprotonation of this salt afforded the corresponding tetradentate P2N2 phosphine−iminophosphorane ligand 1. Coordination to Ni(II) and Pd(II) metal centers afforded complexes 2 and 3, respectively, characterized by multinuclear NMR and X-ray analysis. Both cationic complexes adopt a square-planar geometry around the metal, all phosphorus and nitrogen atoms being coordinated. In contrast to most iminophosphorane complexes, 2 and 3 could be handled in water without any apparent decomposition. Their catalytic activity was evaluated in Suzuki−Miyaura coupling. These reactions were conducted in toluene, water, or a biphasic toluene/water medium in the presence of a phase-transfer agent. Under these last conditions, the Pd catalyst 3 (0.1 mol % catalyst loading) could be reused for five cycles without noticeable loss of activity.
Original languageEnglish
Pages (from-to)4380-4385
Number of pages6
JournalOrganometallics
Volume27
Issue number17
DOIs
Publication statusPublished - 7 Aug 2008

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phosphine
phosphines
ethylenediamine
Metals
Toluene
Ligands
catalysts
ligands
Catalysts
toluene
Water
synthesis
metals
Phosphines
water
Deprotonation
Methane
X ray analysis
nitrogen atoms
Phosphorus

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A mixed phosphine−iminophosphorane tetradentate ligand: Synthesis, coordination to group 10 metal centers, and use as catalyst in Suzuki−Miyaura coupling. / Buchard, Antoine; Komly, Bruno; Auffrant, Audrey; Le Goff, Xavier F.; Floch, Pascal Le.

In: Organometallics, Vol. 27, No. 17, 07.08.2008, p. 4380-4385.

Research output: Contribution to journalArticle

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abstract = "The novel tetradentate ligand 1, associating two phosphines and two iminophosphorane moieties, was easily synthesized from commercially available bis(diphenylphosphino)methane and ethylenediamine via the preparation of the bis(phosphine−aminophosphonium) adduct 1-(HBr)2. Deprotonation of this salt afforded the corresponding tetradentate P2N2 phosphine−iminophosphorane ligand 1. Coordination to Ni(II) and Pd(II) metal centers afforded complexes 2 and 3, respectively, characterized by multinuclear NMR and X-ray analysis. Both cationic complexes adopt a square-planar geometry around the metal, all phosphorus and nitrogen atoms being coordinated. In contrast to most iminophosphorane complexes, 2 and 3 could be handled in water without any apparent decomposition. Their catalytic activity was evaluated in Suzuki−Miyaura coupling. These reactions were conducted in toluene, water, or a biphasic toluene/water medium in the presence of a phase-transfer agent. Under these last conditions, the Pd catalyst 3 (0.1 mol {\%} catalyst loading) could be reused for five cycles without noticeable loss of activity.",
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AU - Floch, Pascal Le

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N2 - The novel tetradentate ligand 1, associating two phosphines and two iminophosphorane moieties, was easily synthesized from commercially available bis(diphenylphosphino)methane and ethylenediamine via the preparation of the bis(phosphine−aminophosphonium) adduct 1-(HBr)2. Deprotonation of this salt afforded the corresponding tetradentate P2N2 phosphine−iminophosphorane ligand 1. Coordination to Ni(II) and Pd(II) metal centers afforded complexes 2 and 3, respectively, characterized by multinuclear NMR and X-ray analysis. Both cationic complexes adopt a square-planar geometry around the metal, all phosphorus and nitrogen atoms being coordinated. In contrast to most iminophosphorane complexes, 2 and 3 could be handled in water without any apparent decomposition. Their catalytic activity was evaluated in Suzuki−Miyaura coupling. These reactions were conducted in toluene, water, or a biphasic toluene/water medium in the presence of a phase-transfer agent. Under these last conditions, the Pd catalyst 3 (0.1 mol % catalyst loading) could be reused for five cycles without noticeable loss of activity.

AB - The novel tetradentate ligand 1, associating two phosphines and two iminophosphorane moieties, was easily synthesized from commercially available bis(diphenylphosphino)methane and ethylenediamine via the preparation of the bis(phosphine−aminophosphonium) adduct 1-(HBr)2. Deprotonation of this salt afforded the corresponding tetradentate P2N2 phosphine−iminophosphorane ligand 1. Coordination to Ni(II) and Pd(II) metal centers afforded complexes 2 and 3, respectively, characterized by multinuclear NMR and X-ray analysis. Both cationic complexes adopt a square-planar geometry around the metal, all phosphorus and nitrogen atoms being coordinated. In contrast to most iminophosphorane complexes, 2 and 3 could be handled in water without any apparent decomposition. Their catalytic activity was evaluated in Suzuki−Miyaura coupling. These reactions were conducted in toluene, water, or a biphasic toluene/water medium in the presence of a phase-transfer agent. Under these last conditions, the Pd catalyst 3 (0.1 mol % catalyst loading) could be reused for five cycles without noticeable loss of activity.

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