Aluminum compounds containing pyrrole-imine ligand systems - Synthesis, characterization, structure elucidation, ring-opening polymerization, and catalytic meerwein-ponndorf-verley reaction

Shu Ya Hsu, Ching Han Hu, Cheng Yi Tu, Chia Her Lin, Ren Yung Chen, Amitabha Datta, Jui Hsien Huang

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Abstract

The reactions of AlMe3 with the tridentate pyrrole ligand precursor C4H3NH(2-CH=NCH2Py) and subsequent treatment of the derivatives with small organic molecules such as 2,6-diisopropylphenol or dibenzoylmethane were conveniently performed, and the products were characterized. The reaction between 1 equiv. of AlMe3 and 1 equiv. of a pyrrole-imine-pyridine ligand in toluene affords [Al{C 4H3N(CHNCH2Py)Me2}] (1) in high yield. In addition, the use of 2 equiv. of AlMe3 with the same tridentate precursor results in the formation of a dialuminum compound [AlMe3{C4H3N(CHNCH2-Py)AlMe 2}] (2) in moderate yield. Furthermore, the combination of 1 with either 1 or 2 equiv. of 2,6-diisopropylphenol or 2 equiv. of dibenzoylmethane in toluene yields aluminum monophenoxide or diphenoxide compounds [Al{C 4H3N(CHNCH2-Py)Me(O-2,6-iPr2C 6H3)}] (3) and [Al{C4H3N(CHNCH 2-Py)}(O-2,6-iPr2C6H3)2] (4), respectively, as well as an aluminum bis-diketonate compound, [Al{C 4H3N(CHNCH2-Py)}(PhCOCHCOPh)2] (5). All of the aforementioned derivatives were characterized by 1H and 13C NMR spectroscopy, and their solid-state molecular structures were determined by single-crystal X-ray diffraction. The geometries of 1-5 show that the pyrrole ligand exists in the pyrrolyl-imine and azafulvene-amido resonance forms. Compounds 1, 3, 4 and 5 were used in the ring-opening polymerization of caprolactone in the presence of BnOH and in the catalytic Meerwein-Ponndorf- Verley (MPV) reaction of 1-naphthalenemethanol and 2-naphthalenecarbaldehyde.

Original languageEnglish
Pages (from-to)1965-1973
Number of pages9
JournalEuropean Journal of Inorganic Chemistry
Issue number11
DOIs
Publication statusPublished - 2014 Apr

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Aluminum Compounds
Pyrroles
Imines
Ring opening polymerization
Toluene
Propofol
Ligands
Aluminum
Derivatives
Molecular structure
Nuclear magnetic resonance spectroscopy
Single crystals
X ray diffraction
Molecules
Geometry
dibenzoylmethane

All Science Journal Classification (ASJC) codes

  • Inorganic Chemistry

Cite this

@article{2e6dcd72caad46c2b8f0f8ab89b467d4,
title = "Aluminum compounds containing pyrrole-imine ligand systems - Synthesis, characterization, structure elucidation, ring-opening polymerization, and catalytic meerwein-ponndorf-verley reaction",
abstract = "The reactions of AlMe3 with the tridentate pyrrole ligand precursor C4H3NH(2-CH=NCH2Py) and subsequent treatment of the derivatives with small organic molecules such as 2,6-diisopropylphenol or dibenzoylmethane were conveniently performed, and the products were characterized. The reaction between 1 equiv. of AlMe3 and 1 equiv. of a pyrrole-imine-pyridine ligand in toluene affords [Al{C 4H3N(CHNCH2Py)Me2}] (1) in high yield. In addition, the use of 2 equiv. of AlMe3 with the same tridentate precursor results in the formation of a dialuminum compound [AlMe3{C4H3N(CHNCH2-Py)AlMe 2}] (2) in moderate yield. Furthermore, the combination of 1 with either 1 or 2 equiv. of 2,6-diisopropylphenol or 2 equiv. of dibenzoylmethane in toluene yields aluminum monophenoxide or diphenoxide compounds [Al{C 4H3N(CHNCH2-Py)Me(O-2,6-iPr2C 6H3)}] (3) and [Al{C4H3N(CHNCH 2-Py)}(O-2,6-iPr2C6H3)2] (4), respectively, as well as an aluminum bis-diketonate compound, [Al{C 4H3N(CHNCH2-Py)}(PhCOCHCOPh)2] (5). All of the aforementioned derivatives were characterized by 1H and 13C NMR spectroscopy, and their solid-state molecular structures were determined by single-crystal X-ray diffraction. The geometries of 1-5 show that the pyrrole ligand exists in the pyrrolyl-imine and azafulvene-amido resonance forms. Compounds 1, 3, 4 and 5 were used in the ring-opening polymerization of caprolactone in the presence of BnOH and in the catalytic Meerwein-Ponndorf- Verley (MPV) reaction of 1-naphthalenemethanol and 2-naphthalenecarbaldehyde.",
author = "Hsu, {Shu Ya} and Hu, {Ching Han} and Tu, {Cheng Yi} and Lin, {Chia Her} and Chen, {Ren Yung} and Amitabha Datta and Huang, {Jui Hsien}",
year = "2014",
month = "4",
doi = "10.1002/ejic.201400082",
language = "English",
pages = "1965--1973",
journal = "Chemische Berichte",
issn = "0009-2940",
publisher = "Wiley-VCH Verlag",
number = "11",

}

TY - JOUR

T1 - Aluminum compounds containing pyrrole-imine ligand systems - Synthesis, characterization, structure elucidation, ring-opening polymerization, and catalytic meerwein-ponndorf-verley reaction

AU - Hsu, Shu Ya

AU - Hu, Ching Han

AU - Tu, Cheng Yi

AU - Lin, Chia Her

AU - Chen, Ren Yung

AU - Datta, Amitabha

AU - Huang, Jui Hsien

PY - 2014/4

Y1 - 2014/4

N2 - The reactions of AlMe3 with the tridentate pyrrole ligand precursor C4H3NH(2-CH=NCH2Py) and subsequent treatment of the derivatives with small organic molecules such as 2,6-diisopropylphenol or dibenzoylmethane were conveniently performed, and the products were characterized. The reaction between 1 equiv. of AlMe3 and 1 equiv. of a pyrrole-imine-pyridine ligand in toluene affords [Al{C 4H3N(CHNCH2Py)Me2}] (1) in high yield. In addition, the use of 2 equiv. of AlMe3 with the same tridentate precursor results in the formation of a dialuminum compound [AlMe3{C4H3N(CHNCH2-Py)AlMe 2}] (2) in moderate yield. Furthermore, the combination of 1 with either 1 or 2 equiv. of 2,6-diisopropylphenol or 2 equiv. of dibenzoylmethane in toluene yields aluminum monophenoxide or diphenoxide compounds [Al{C 4H3N(CHNCH2-Py)Me(O-2,6-iPr2C 6H3)}] (3) and [Al{C4H3N(CHNCH 2-Py)}(O-2,6-iPr2C6H3)2] (4), respectively, as well as an aluminum bis-diketonate compound, [Al{C 4H3N(CHNCH2-Py)}(PhCOCHCOPh)2] (5). All of the aforementioned derivatives were characterized by 1H and 13C NMR spectroscopy, and their solid-state molecular structures were determined by single-crystal X-ray diffraction. The geometries of 1-5 show that the pyrrole ligand exists in the pyrrolyl-imine and azafulvene-amido resonance forms. Compounds 1, 3, 4 and 5 were used in the ring-opening polymerization of caprolactone in the presence of BnOH and in the catalytic Meerwein-Ponndorf- Verley (MPV) reaction of 1-naphthalenemethanol and 2-naphthalenecarbaldehyde.

AB - The reactions of AlMe3 with the tridentate pyrrole ligand precursor C4H3NH(2-CH=NCH2Py) and subsequent treatment of the derivatives with small organic molecules such as 2,6-diisopropylphenol or dibenzoylmethane were conveniently performed, and the products were characterized. The reaction between 1 equiv. of AlMe3 and 1 equiv. of a pyrrole-imine-pyridine ligand in toluene affords [Al{C 4H3N(CHNCH2Py)Me2}] (1) in high yield. In addition, the use of 2 equiv. of AlMe3 with the same tridentate precursor results in the formation of a dialuminum compound [AlMe3{C4H3N(CHNCH2-Py)AlMe 2}] (2) in moderate yield. Furthermore, the combination of 1 with either 1 or 2 equiv. of 2,6-diisopropylphenol or 2 equiv. of dibenzoylmethane in toluene yields aluminum monophenoxide or diphenoxide compounds [Al{C 4H3N(CHNCH2-Py)Me(O-2,6-iPr2C 6H3)}] (3) and [Al{C4H3N(CHNCH 2-Py)}(O-2,6-iPr2C6H3)2] (4), respectively, as well as an aluminum bis-diketonate compound, [Al{C 4H3N(CHNCH2-Py)}(PhCOCHCOPh)2] (5). All of the aforementioned derivatives were characterized by 1H and 13C NMR spectroscopy, and their solid-state molecular structures were determined by single-crystal X-ray diffraction. The geometries of 1-5 show that the pyrrole ligand exists in the pyrrolyl-imine and azafulvene-amido resonance forms. Compounds 1, 3, 4 and 5 were used in the ring-opening polymerization of caprolactone in the presence of BnOH and in the catalytic Meerwein-Ponndorf- Verley (MPV) reaction of 1-naphthalenemethanol and 2-naphthalenecarbaldehyde.

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JF - Chemische Berichte

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