Unsaturated Pd(0), Pd(I), and Pd(II) complexes of a new methoxy-substituted benzyl phosphine. Aryl-X (X = Cl, I) oxidative addition, C-O cleavage, and Suzuki-Miyaura coupling of aryl chlorides

Haim Weissman, Linda J W Shimon, David Milstein

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Abstract

The 14e- Pd(0)L2 complex 2 was prepared by reduction of [Pd(2-methylallyl)Cl]2 in the presence of the new, electron-rich, bulky methoxy benzyl phosphine (dmobp) ligand 1. Structural characterization of this complex indicates that the methoxy groups are not coordinated to the metal center. Complex 2 undergoes oxidative addition of iodo- and chlorobenzene at room temperature to yield the monophosphine complexes LPd(Ph)X (4, X = I; 5, X = Cl) in which the methoxy group is coordinated to the Pd(II) center in the solid state, as indicated by the X-ray structure of 4. In solution there is no evidence for methoxy coordination, indicating the availability of a Pd(II) 14e- complex. The Me-O bond in 4 is longer than the corresponding bond in 2, indicating that coordination of the methoxy group weakens the C-O bond. Reaction of complex 4 or 5 with the free ligand 1 results in nucleophilic attack and C-O cleavage, leading to the dimeric phenoxy-bridged complex 7, which was structurally characterized. Partial reduction of [Pd(2-methylallyl)Cl] 2 in the presence of the ligand 1 leads to the Pd(I) dimer 3, which can be converted to the Pd(0) complex 2 by addition of ligand 1 and a base. This complex, which bears only one phosphine for each Pd atom, is a suitable precursor to a presumed catalytically active 12e- Pd(0) catalyst, Complexes 2 and 3 catalyze the Suzuki-Miyaura cross-coupling of chlorobenzene with PhB(OH)2 even at room temperature, albeit slowly, while the C-O cleaved phenoxy-bridged complex 7 is not catalytically active at 40°C, indicating that it is not an intermediate in the catalysis. The dmobp ligand 1 is more effective in Suzuki-Miyaura coupling than an analogous benzyl ligand lacking methoxy substituents.

Original languageEnglish
Pages (from-to)3931-3940
Number of pages10
JournalOrganometallics
Volume23
Issue number16
DOIs
Publication statusPublished - Aug 2 2004

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phosphine
phosphines
Chlorides
cleavage
chlorides
Ligands
ligands
chlorobenzenes
cross coupling
room temperature
bears
Dimers
Catalysis
attack
catalysis
availability
Metals
dimers

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

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@article{66b2f8f95dcf4d0aab71e59c0b305f94,
title = "Unsaturated Pd(0), Pd(I), and Pd(II) complexes of a new methoxy-substituted benzyl phosphine. Aryl-X (X = Cl, I) oxidative addition, C-O cleavage, and Suzuki-Miyaura coupling of aryl chlorides",
abstract = "The 14e- Pd(0)L2 complex 2 was prepared by reduction of [Pd(2-methylallyl)Cl]2 in the presence of the new, electron-rich, bulky methoxy benzyl phosphine (dmobp) ligand 1. Structural characterization of this complex indicates that the methoxy groups are not coordinated to the metal center. Complex 2 undergoes oxidative addition of iodo- and chlorobenzene at room temperature to yield the monophosphine complexes LPd(Ph)X (4, X = I; 5, X = Cl) in which the methoxy group is coordinated to the Pd(II) center in the solid state, as indicated by the X-ray structure of 4. In solution there is no evidence for methoxy coordination, indicating the availability of a Pd(II) 14e- complex. The Me-O bond in 4 is longer than the corresponding bond in 2, indicating that coordination of the methoxy group weakens the C-O bond. Reaction of complex 4 or 5 with the free ligand 1 results in nucleophilic attack and C-O cleavage, leading to the dimeric phenoxy-bridged complex 7, which was structurally characterized. Partial reduction of [Pd(2-methylallyl)Cl] 2 in the presence of the ligand 1 leads to the Pd(I) dimer 3, which can be converted to the Pd(0) complex 2 by addition of ligand 1 and a base. This complex, which bears only one phosphine for each Pd atom, is a suitable precursor to a presumed catalytically active 12e- Pd(0) catalyst, Complexes 2 and 3 catalyze the Suzuki-Miyaura cross-coupling of chlorobenzene with PhB(OH)2 even at room temperature, albeit slowly, while the C-O cleaved phenoxy-bridged complex 7 is not catalytically active at 40°C, indicating that it is not an intermediate in the catalysis. The dmobp ligand 1 is more effective in Suzuki-Miyaura coupling than an analogous benzyl ligand lacking methoxy substituents.",
author = "Haim Weissman and Shimon, {Linda J W} and David Milstein",
year = "2004",
month = "8",
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doi = "10.1021/om0497588",
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T1 - Unsaturated Pd(0), Pd(I), and Pd(II) complexes of a new methoxy-substituted benzyl phosphine. Aryl-X (X = Cl, I) oxidative addition, C-O cleavage, and Suzuki-Miyaura coupling of aryl chlorides

AU - Weissman, Haim

AU - Shimon, Linda J W

AU - Milstein, David

PY - 2004/8/2

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N2 - The 14e- Pd(0)L2 complex 2 was prepared by reduction of [Pd(2-methylallyl)Cl]2 in the presence of the new, electron-rich, bulky methoxy benzyl phosphine (dmobp) ligand 1. Structural characterization of this complex indicates that the methoxy groups are not coordinated to the metal center. Complex 2 undergoes oxidative addition of iodo- and chlorobenzene at room temperature to yield the monophosphine complexes LPd(Ph)X (4, X = I; 5, X = Cl) in which the methoxy group is coordinated to the Pd(II) center in the solid state, as indicated by the X-ray structure of 4. In solution there is no evidence for methoxy coordination, indicating the availability of a Pd(II) 14e- complex. The Me-O bond in 4 is longer than the corresponding bond in 2, indicating that coordination of the methoxy group weakens the C-O bond. Reaction of complex 4 or 5 with the free ligand 1 results in nucleophilic attack and C-O cleavage, leading to the dimeric phenoxy-bridged complex 7, which was structurally characterized. Partial reduction of [Pd(2-methylallyl)Cl] 2 in the presence of the ligand 1 leads to the Pd(I) dimer 3, which can be converted to the Pd(0) complex 2 by addition of ligand 1 and a base. This complex, which bears only one phosphine for each Pd atom, is a suitable precursor to a presumed catalytically active 12e- Pd(0) catalyst, Complexes 2 and 3 catalyze the Suzuki-Miyaura cross-coupling of chlorobenzene with PhB(OH)2 even at room temperature, albeit slowly, while the C-O cleaved phenoxy-bridged complex 7 is not catalytically active at 40°C, indicating that it is not an intermediate in the catalysis. The dmobp ligand 1 is more effective in Suzuki-Miyaura coupling than an analogous benzyl ligand lacking methoxy substituents.

AB - The 14e- Pd(0)L2 complex 2 was prepared by reduction of [Pd(2-methylallyl)Cl]2 in the presence of the new, electron-rich, bulky methoxy benzyl phosphine (dmobp) ligand 1. Structural characterization of this complex indicates that the methoxy groups are not coordinated to the metal center. Complex 2 undergoes oxidative addition of iodo- and chlorobenzene at room temperature to yield the monophosphine complexes LPd(Ph)X (4, X = I; 5, X = Cl) in which the methoxy group is coordinated to the Pd(II) center in the solid state, as indicated by the X-ray structure of 4. In solution there is no evidence for methoxy coordination, indicating the availability of a Pd(II) 14e- complex. The Me-O bond in 4 is longer than the corresponding bond in 2, indicating that coordination of the methoxy group weakens the C-O bond. Reaction of complex 4 or 5 with the free ligand 1 results in nucleophilic attack and C-O cleavage, leading to the dimeric phenoxy-bridged complex 7, which was structurally characterized. Partial reduction of [Pd(2-methylallyl)Cl] 2 in the presence of the ligand 1 leads to the Pd(I) dimer 3, which can be converted to the Pd(0) complex 2 by addition of ligand 1 and a base. This complex, which bears only one phosphine for each Pd atom, is a suitable precursor to a presumed catalytically active 12e- Pd(0) catalyst, Complexes 2 and 3 catalyze the Suzuki-Miyaura cross-coupling of chlorobenzene with PhB(OH)2 even at room temperature, albeit slowly, while the C-O cleaved phenoxy-bridged complex 7 is not catalytically active at 40°C, indicating that it is not an intermediate in the catalysis. The dmobp ligand 1 is more effective in Suzuki-Miyaura coupling than an analogous benzyl ligand lacking methoxy substituents.

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