Reactions of dimeric aluminium hydride compounds containing bidentate dianionic pyrrolyl ligands and their applications in ring-opening polymerization of ε-caprolactone

Ya Chi Chen, Che Yu Lin, Wen Yen Huang, Amitabha Datta, Jui-Hsien Huang, Meng Shiue Tsai, Ting Yu Lee, Cheng Yi Tu, Ching-Han Hu

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Abstract

A series of dimeric aluminium compounds containing substituted bidentate dianionic pyrrolyl ligands have been synthesized and their reactivity and application in the ring-opening polymerization of ε-caprolactone have been studied. The reactions of [{C4H3N(2-CH2NtBu)} AlH]2 (1) with 2 equiv. of 1-indanone and 9-fluorenone in dichloromethane generated [{C4H3N(2-CH2NtBu)} Al(μ-OC9H9)]2 (2) and [{C4H 3N(2-CH2NtBu)}Al{μ-OCH(C12H 8)}]2 (3), respectively, by hydroalumination. Similarly, the reactions of 1 with 2 equiv. of 2-cyclohexen-1-one, 1-(2,4,6- trimethylphenyl)-1-ethanone, benzophenone, and 1,1-diphenylacetone in dichloromethane afforded NtBu-bridged dialuminium compounds 4-7, [{C 4H3N(2-CH2NtBu)}Al(OR)]2 [4, R = C6H9; 5, R = CH(Me)(C6H2-2,4,6- Me3); 6, R = CHPh2; 7, R = CH(Me)(CHPh2)] by insertion. A similar insertion occurred when 1 was treated with 2 equiv. of 2,4-pentandione and dibenzoylmethane in dichloromethane to yield NtBu-bridged dioxylate aluminium dimeric compounds 8 and 9, respectively. The Al atoms in compounds 2 and 4-7 possess a distorted tetrahedral geometry whereas the Al atoms in 8 and 9 have a square-pyramidal environment. All the compounds have been well characterized by NMR spectroscopy and compounds 2 and 4-9 in the solid state were subjected to X-ray diffraction analysis. A study of the polymerization of ε-caprolactone revealed that the activity of the Al complexes is largely reliant on the steric nature of the substituents of their alkoxide groups.

Original languageEnglish
Pages (from-to)2459-2469
Number of pages11
JournalEuropean Journal of Inorganic Chemistry
Issue number15
DOIs
Publication statusPublished - 2011 May 1

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Methylene Chloride
Ring opening polymerization
Aluminum
Hydrides
Ligands
Aluminum Compounds
Aluminum compounds
Atoms
X ray diffraction analysis
Nuclear magnetic resonance spectroscopy
Polymerization
Geometry
caprolactone

All Science Journal Classification (ASJC) codes

  • Inorganic Chemistry

Cite this

@article{29c5fd4356474d688b8dcea54613e448,
title = "Reactions of dimeric aluminium hydride compounds containing bidentate dianionic pyrrolyl ligands and their applications in ring-opening polymerization of ε-caprolactone",
abstract = "A series of dimeric aluminium compounds containing substituted bidentate dianionic pyrrolyl ligands have been synthesized and their reactivity and application in the ring-opening polymerization of ε-caprolactone have been studied. The reactions of [{C4H3N(2-CH2NtBu)} AlH]2 (1) with 2 equiv. of 1-indanone and 9-fluorenone in dichloromethane generated [{C4H3N(2-CH2NtBu)} Al(μ-OC9H9)]2 (2) and [{C4H 3N(2-CH2NtBu)}Al{μ-OCH(C12H 8)}]2 (3), respectively, by hydroalumination. Similarly, the reactions of 1 with 2 equiv. of 2-cyclohexen-1-one, 1-(2,4,6- trimethylphenyl)-1-ethanone, benzophenone, and 1,1-diphenylacetone in dichloromethane afforded NtBu-bridged dialuminium compounds 4-7, [{C 4H3N(2-CH2NtBu)}Al(OR)]2 [4, R = C6H9; 5, R = CH(Me)(C6H2-2,4,6- Me3); 6, R = CHPh2; 7, R = CH(Me)(CHPh2)] by insertion. A similar insertion occurred when 1 was treated with 2 equiv. of 2,4-pentandione and dibenzoylmethane in dichloromethane to yield NtBu-bridged dioxylate aluminium dimeric compounds 8 and 9, respectively. The Al atoms in compounds 2 and 4-7 possess a distorted tetrahedral geometry whereas the Al atoms in 8 and 9 have a square-pyramidal environment. All the compounds have been well characterized by NMR spectroscopy and compounds 2 and 4-9 in the solid state were subjected to X-ray diffraction analysis. A study of the polymerization of ε-caprolactone revealed that the activity of the Al complexes is largely reliant on the steric nature of the substituents of their alkoxide groups.",
author = "Chen, {Ya Chi} and Lin, {Che Yu} and Huang, {Wen Yen} and Amitabha Datta and Jui-Hsien Huang and Tsai, {Meng Shiue} and Lee, {Ting Yu} and Tu, {Cheng Yi} and Ching-Han Hu",
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Reactions of dimeric aluminium hydride compounds containing bidentate dianionic pyrrolyl ligands and their applications in ring-opening polymerization of ε-caprolactone. / Chen, Ya Chi; Lin, Che Yu; Huang, Wen Yen; Datta, Amitabha; Huang, Jui-Hsien; Tsai, Meng Shiue; Lee, Ting Yu; Tu, Cheng Yi; Hu, Ching-Han.

In: European Journal of Inorganic Chemistry, No. 15, 01.05.2011, p. 2459-2469.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Reactions of dimeric aluminium hydride compounds containing bidentate dianionic pyrrolyl ligands and their applications in ring-opening polymerization of ε-caprolactone

AU - Chen, Ya Chi

AU - Lin, Che Yu

AU - Huang, Wen Yen

AU - Datta, Amitabha

AU - Huang, Jui-Hsien

AU - Tsai, Meng Shiue

AU - Lee, Ting Yu

AU - Tu, Cheng Yi

AU - Hu, Ching-Han

PY - 2011/5/1

Y1 - 2011/5/1

N2 - A series of dimeric aluminium compounds containing substituted bidentate dianionic pyrrolyl ligands have been synthesized and their reactivity and application in the ring-opening polymerization of ε-caprolactone have been studied. The reactions of [{C4H3N(2-CH2NtBu)} AlH]2 (1) with 2 equiv. of 1-indanone and 9-fluorenone in dichloromethane generated [{C4H3N(2-CH2NtBu)} Al(μ-OC9H9)]2 (2) and [{C4H 3N(2-CH2NtBu)}Al{μ-OCH(C12H 8)}]2 (3), respectively, by hydroalumination. Similarly, the reactions of 1 with 2 equiv. of 2-cyclohexen-1-one, 1-(2,4,6- trimethylphenyl)-1-ethanone, benzophenone, and 1,1-diphenylacetone in dichloromethane afforded NtBu-bridged dialuminium compounds 4-7, [{C 4H3N(2-CH2NtBu)}Al(OR)]2 [4, R = C6H9; 5, R = CH(Me)(C6H2-2,4,6- Me3); 6, R = CHPh2; 7, R = CH(Me)(CHPh2)] by insertion. A similar insertion occurred when 1 was treated with 2 equiv. of 2,4-pentandione and dibenzoylmethane in dichloromethane to yield NtBu-bridged dioxylate aluminium dimeric compounds 8 and 9, respectively. The Al atoms in compounds 2 and 4-7 possess a distorted tetrahedral geometry whereas the Al atoms in 8 and 9 have a square-pyramidal environment. All the compounds have been well characterized by NMR spectroscopy and compounds 2 and 4-9 in the solid state were subjected to X-ray diffraction analysis. A study of the polymerization of ε-caprolactone revealed that the activity of the Al complexes is largely reliant on the steric nature of the substituents of their alkoxide groups.

AB - A series of dimeric aluminium compounds containing substituted bidentate dianionic pyrrolyl ligands have been synthesized and their reactivity and application in the ring-opening polymerization of ε-caprolactone have been studied. The reactions of [{C4H3N(2-CH2NtBu)} AlH]2 (1) with 2 equiv. of 1-indanone and 9-fluorenone in dichloromethane generated [{C4H3N(2-CH2NtBu)} Al(μ-OC9H9)]2 (2) and [{C4H 3N(2-CH2NtBu)}Al{μ-OCH(C12H 8)}]2 (3), respectively, by hydroalumination. Similarly, the reactions of 1 with 2 equiv. of 2-cyclohexen-1-one, 1-(2,4,6- trimethylphenyl)-1-ethanone, benzophenone, and 1,1-diphenylacetone in dichloromethane afforded NtBu-bridged dialuminium compounds 4-7, [{C 4H3N(2-CH2NtBu)}Al(OR)]2 [4, R = C6H9; 5, R = CH(Me)(C6H2-2,4,6- Me3); 6, R = CHPh2; 7, R = CH(Me)(CHPh2)] by insertion. A similar insertion occurred when 1 was treated with 2 equiv. of 2,4-pentandione and dibenzoylmethane in dichloromethane to yield NtBu-bridged dioxylate aluminium dimeric compounds 8 and 9, respectively. The Al atoms in compounds 2 and 4-7 possess a distorted tetrahedral geometry whereas the Al atoms in 8 and 9 have a square-pyramidal environment. All the compounds have been well characterized by NMR spectroscopy and compounds 2 and 4-9 in the solid state were subjected to X-ray diffraction analysis. A study of the polymerization of ε-caprolactone revealed that the activity of the Al complexes is largely reliant on the steric nature of the substituents of their alkoxide groups.

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