Synthesis and protonolysis of neutral aluminum dihydride compounds stabilized by tridentate-substituted pyrrolyl ligands: Synthesis, structural characterization and ring-opening polymerization of ε-caprolactone

Jr Chiuan Chang, Ya Chi Chen, Amitabha Datta, Chia Her Lin, Ching Sheng Hsiao, Jui Hsien Huang

Research output: Contribution to journalArticle

18 Citations (Scopus)

Abstract

A series of aluminum compounds containing tridentate pyrrolyl ligands were obtained from related aluminum dihydride compounds via protonolysis. Treatment of tetranuclear aluminum compound [C4H2N{2,5-(CH 2NMe2)2}Al2H5] 2 (1) with two equivalents of [C4H3N{2,5- (CH2NMe2)2}] in methylene chloride at 0 °C led to the formation of [C4H2N{2,5-(CH2NMe 2)2}]AlH2 (2). Similarly, when the deuterated aluminum compound 1D was used, the corresponding aluminum compound [C 4H2N{2,5-(CH2NMe2) 2}]AlD2 (2D) could be isolated. The reaction of 2 with one or two equivalents of phenylethyne, triphenylmethanethiol, 2,6- diisopropylaniline, or triphenylsilanol generated mononuclear aluminum compounds [[C4H2N{2,5-(CH2NMe2) 2}]AlRR′ (3, R = -CCPh, R′ = H; 4, R = R′ = -CCPh; 5, R = -SCPh3, R′ = H; 6, R = R′ = -SCPh3; 7, R = -NH(2,6-iPr2Ph), R′ = H; 8, R = R′ = -NH(2,6-iPr2Ph); 9, R = -OSiPh3, R′ = H; 10, R = R′ = -OSiPh3). Related Al-D compounds of 3, 5, 7 and 9 were also synthesized and corresponding IR spectroscopic data well matched in comparison of the stretching frequencies of Al-H and Al-D. The molecular structures of 2D, 4, 5, 5D, 7, and 10 have been determined by X-ray crystallography. Compounds 2, 5, and 7 initiated the ring-opening polymerization of ε-caprolactone and produced high-molecular weight of poly-ε-caprolactone.

Original languageEnglish
Pages (from-to)3673-3680
Number of pages8
JournalJournal of Organometallic Chemistry
Volume696
Issue number23
DOIs
Publication statusPublished - 2011 Nov 15

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Aluminum Compounds
Aluminum compounds
aluminum compounds
dihydrides
Ring opening polymerization
Polymerization
polymerization
Ligands
aluminum
ligands
rings
synthesis
Methylene Chloride
X ray crystallography
methylene
X Ray Crystallography
Molecular structure
Dichloromethane
Stretching
crystallography

All Science Journal Classification (ASJC) codes

  • Biochemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

Cite this

@article{72bba9dcabeb42e2be1d5057ee05e3b8,
title = "Synthesis and protonolysis of neutral aluminum dihydride compounds stabilized by tridentate-substituted pyrrolyl ligands: Synthesis, structural characterization and ring-opening polymerization of ε-caprolactone",
abstract = "A series of aluminum compounds containing tridentate pyrrolyl ligands were obtained from related aluminum dihydride compounds via protonolysis. Treatment of tetranuclear aluminum compound [C4H2N{2,5-(CH 2NMe2)2}Al2H5] 2 (1) with two equivalents of [C4H3N{2,5- (CH2NMe2)2}] in methylene chloride at 0 °C led to the formation of [C4H2N{2,5-(CH2NMe 2)2}]AlH2 (2). Similarly, when the deuterated aluminum compound 1D was used, the corresponding aluminum compound [C 4H2N{2,5-(CH2NMe2) 2}]AlD2 (2D) could be isolated. The reaction of 2 with one or two equivalents of phenylethyne, triphenylmethanethiol, 2,6- diisopropylaniline, or triphenylsilanol generated mononuclear aluminum compounds [[C4H2N{2,5-(CH2NMe2) 2}]AlRR′ (3, R = -CCPh, R′ = H; 4, R = R′ = -CCPh; 5, R = -SCPh3, R′ = H; 6, R = R′ = -SCPh3; 7, R = -NH(2,6-iPr2Ph), R′ = H; 8, R = R′ = -NH(2,6-iPr2Ph); 9, R = -OSiPh3, R′ = H; 10, R = R′ = -OSiPh3). Related Al-D compounds of 3, 5, 7 and 9 were also synthesized and corresponding IR spectroscopic data well matched in comparison of the stretching frequencies of Al-H and Al-D. The molecular structures of 2D, 4, 5, 5D, 7, and 10 have been determined by X-ray crystallography. Compounds 2, 5, and 7 initiated the ring-opening polymerization of ε-caprolactone and produced high-molecular weight of poly-ε-caprolactone.",
author = "Chang, {Jr Chiuan} and Chen, {Ya Chi} and Amitabha Datta and Lin, {Chia Her} and Hsiao, {Ching Sheng} and Huang, {Jui Hsien}",
year = "2011",
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language = "English",
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pages = "3673--3680",
journal = "Journal of Organometallic Chemistry",
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Synthesis and protonolysis of neutral aluminum dihydride compounds stabilized by tridentate-substituted pyrrolyl ligands : Synthesis, structural characterization and ring-opening polymerization of ε-caprolactone. / Chang, Jr Chiuan; Chen, Ya Chi; Datta, Amitabha; Lin, Chia Her; Hsiao, Ching Sheng; Huang, Jui Hsien.

In: Journal of Organometallic Chemistry, Vol. 696, No. 23, 15.11.2011, p. 3673-3680.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Synthesis and protonolysis of neutral aluminum dihydride compounds stabilized by tridentate-substituted pyrrolyl ligands

T2 - Synthesis, structural characterization and ring-opening polymerization of ε-caprolactone

AU - Chang, Jr Chiuan

AU - Chen, Ya Chi

AU - Datta, Amitabha

AU - Lin, Chia Her

AU - Hsiao, Ching Sheng

AU - Huang, Jui Hsien

PY - 2011/11/15

Y1 - 2011/11/15

N2 - A series of aluminum compounds containing tridentate pyrrolyl ligands were obtained from related aluminum dihydride compounds via protonolysis. Treatment of tetranuclear aluminum compound [C4H2N{2,5-(CH 2NMe2)2}Al2H5] 2 (1) with two equivalents of [C4H3N{2,5- (CH2NMe2)2}] in methylene chloride at 0 °C led to the formation of [C4H2N{2,5-(CH2NMe 2)2}]AlH2 (2). Similarly, when the deuterated aluminum compound 1D was used, the corresponding aluminum compound [C 4H2N{2,5-(CH2NMe2) 2}]AlD2 (2D) could be isolated. The reaction of 2 with one or two equivalents of phenylethyne, triphenylmethanethiol, 2,6- diisopropylaniline, or triphenylsilanol generated mononuclear aluminum compounds [[C4H2N{2,5-(CH2NMe2) 2}]AlRR′ (3, R = -CCPh, R′ = H; 4, R = R′ = -CCPh; 5, R = -SCPh3, R′ = H; 6, R = R′ = -SCPh3; 7, R = -NH(2,6-iPr2Ph), R′ = H; 8, R = R′ = -NH(2,6-iPr2Ph); 9, R = -OSiPh3, R′ = H; 10, R = R′ = -OSiPh3). Related Al-D compounds of 3, 5, 7 and 9 were also synthesized and corresponding IR spectroscopic data well matched in comparison of the stretching frequencies of Al-H and Al-D. The molecular structures of 2D, 4, 5, 5D, 7, and 10 have been determined by X-ray crystallography. Compounds 2, 5, and 7 initiated the ring-opening polymerization of ε-caprolactone and produced high-molecular weight of poly-ε-caprolactone.

AB - A series of aluminum compounds containing tridentate pyrrolyl ligands were obtained from related aluminum dihydride compounds via protonolysis. Treatment of tetranuclear aluminum compound [C4H2N{2,5-(CH 2NMe2)2}Al2H5] 2 (1) with two equivalents of [C4H3N{2,5- (CH2NMe2)2}] in methylene chloride at 0 °C led to the formation of [C4H2N{2,5-(CH2NMe 2)2}]AlH2 (2). Similarly, when the deuterated aluminum compound 1D was used, the corresponding aluminum compound [C 4H2N{2,5-(CH2NMe2) 2}]AlD2 (2D) could be isolated. The reaction of 2 with one or two equivalents of phenylethyne, triphenylmethanethiol, 2,6- diisopropylaniline, or triphenylsilanol generated mononuclear aluminum compounds [[C4H2N{2,5-(CH2NMe2) 2}]AlRR′ (3, R = -CCPh, R′ = H; 4, R = R′ = -CCPh; 5, R = -SCPh3, R′ = H; 6, R = R′ = -SCPh3; 7, R = -NH(2,6-iPr2Ph), R′ = H; 8, R = R′ = -NH(2,6-iPr2Ph); 9, R = -OSiPh3, R′ = H; 10, R = R′ = -OSiPh3). Related Al-D compounds of 3, 5, 7 and 9 were also synthesized and corresponding IR spectroscopic data well matched in comparison of the stretching frequencies of Al-H and Al-D. The molecular structures of 2D, 4, 5, 5D, 7, and 10 have been determined by X-ray crystallography. Compounds 2, 5, and 7 initiated the ring-opening polymerization of ε-caprolactone and produced high-molecular weight of poly-ε-caprolactone.

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U2 - 10.1016/j.jorganchem.2011.08.021

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JF - Journal of Organometallic Chemistry

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