New types of bi- and tri-dentate pyrrole-piperazine ligands and related zinc compounds: Synthesis, characterization, reaction study, and ring-opening polymerization of ε-caprolactone

Ming Chun Wu, Ting Chia Hu, Ya Chun Lo, Ting Yu Lee, Chia Her Lin, Wei Yi Lu, Chu Chieh Lin, Amitabha Datta, Jui-Hsien Huang

Research output: Contribution to journalArticle

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Abstract

Reactions of one or two equivalents of formaldehyde and phenylpiperazine with pyrrole in methanol or ethanol generated substituted pyrrole ligands C4H3NH-[2-CH2N(CH2CH2)2NPh] (1) and C4H2NH-{2,5-[CH2N(CH2CH2)2NPh]2} (2), respectively. Reacting 1 with one equivalent of ZnMe2 in toluene generated a di-zinc compound 3, {ZnMe{C4H3N-[2-CH2N(CH2CH2)2NPh]}}2, in moderate yield. Further reacting 3 with two equivalents of p-cresol in toluene overnight afforded pheoxide bridged di-zinc compound 4, {Zn(μ-O-C6H4-4-Me){C4H3N-[2-CH2N(CH2CH2)2NPh]}}2. Similarly, the reactions of one and two equivalents of tridentate substituted pyrrole ligand 2 with ZnMe2 afforded Zn compounds ZnMe{C4H2N-{2,5-[CH2N(CH2CH2)2NPh]2}} (5) and Zn{C4H2N-{2,5-[CH2N(CH2CH2)2NPh]2}}2 (6), respectively, in moderate yield. All of these compounds were characterized using 1H and 13C NMR spectroscopy. Compound 5 is relatively air and moisture sensitive and decomposes during the recrystallization process to yield a tri-Zn cluster, {Zn(μ2-OH){C4H2N-{2,5-[CH2N(CH2CH2)2NPh]2}}}3 (7). The molecular geometries of compounds 1, 3, 4, 6, and 7 were also determined using single crystal X-ray diffractometric analysis. Compounds 3, 4, and 6 were used as initiators for the ring opening polymerization of ε-caprolactone, and all of the zinc compounds showed high conversion with broad or bimodal molecular weight distributions.

Original languageEnglish
Pages (from-to)141-147
Number of pages7
JournalJournal of Organometallic Chemistry
Volume791
DOIs
Publication statusPublished - 2015 Jun 12

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Zinc Compounds
Zinc compounds
zinc compounds
Pyrroles
Ring opening polymerization
pyrroles
Polymerization
polymerization
Ligands
Toluene
ligands
toluene
rings
synthesis
cresols
X ray analysis
initiators
Molecular weight distribution
formaldehyde
Formaldehyde

All Science Journal Classification (ASJC) codes

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

Cite this

Wu, Ming Chun ; Hu, Ting Chia ; Lo, Ya Chun ; Lee, Ting Yu ; Lin, Chia Her ; Lu, Wei Yi ; Lin, Chu Chieh ; Datta, Amitabha ; Huang, Jui-Hsien. / New types of bi- and tri-dentate pyrrole-piperazine ligands and related zinc compounds : Synthesis, characterization, reaction study, and ring-opening polymerization of ε-caprolactone. In: Journal of Organometallic Chemistry. 2015 ; Vol. 791. pp. 141-147.
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title = "New types of bi- and tri-dentate pyrrole-piperazine ligands and related zinc compounds: Synthesis, characterization, reaction study, and ring-opening polymerization of ε-caprolactone",
abstract = "Reactions of one or two equivalents of formaldehyde and phenylpiperazine with pyrrole in methanol or ethanol generated substituted pyrrole ligands C4H3NH-[2-CH2N(CH2CH2)2NPh] (1) and C4H2NH-{2,5-[CH2N(CH2CH2)2NPh]2} (2), respectively. Reacting 1 with one equivalent of ZnMe2 in toluene generated a di-zinc compound 3, {ZnMe{C4H3N-[2-CH2N(CH2CH2)2NPh]}}2, in moderate yield. Further reacting 3 with two equivalents of p-cresol in toluene overnight afforded pheoxide bridged di-zinc compound 4, {Zn(μ-O-C6H4-4-Me){C4H3N-[2-CH2N(CH2CH2)2NPh]}}2. Similarly, the reactions of one and two equivalents of tridentate substituted pyrrole ligand 2 with ZnMe2 afforded Zn compounds ZnMe{C4H2N-{2,5-[CH2N(CH2CH2)2NPh]2}} (5) and Zn{C4H2N-{2,5-[CH2N(CH2CH2)2NPh]2}}2 (6), respectively, in moderate yield. All of these compounds were characterized using 1H and 13C NMR spectroscopy. Compound 5 is relatively air and moisture sensitive and decomposes during the recrystallization process to yield a tri-Zn cluster, {Zn(μ2-OH){C4H2N-{2,5-[CH2N(CH2CH2)2NPh]2}}}3 (7). The molecular geometries of compounds 1, 3, 4, 6, and 7 were also determined using single crystal X-ray diffractometric analysis. Compounds 3, 4, and 6 were used as initiators for the ring opening polymerization of ε-caprolactone, and all of the zinc compounds showed high conversion with broad or bimodal molecular weight distributions.",
author = "Wu, {Ming Chun} and Hu, {Ting Chia} and Lo, {Ya Chun} and Lee, {Ting Yu} and Lin, {Chia Her} and Lu, {Wei Yi} and Lin, {Chu Chieh} and Amitabha Datta and Jui-Hsien Huang",
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New types of bi- and tri-dentate pyrrole-piperazine ligands and related zinc compounds : Synthesis, characterization, reaction study, and ring-opening polymerization of ε-caprolactone. / Wu, Ming Chun; Hu, Ting Chia; Lo, Ya Chun; Lee, Ting Yu; Lin, Chia Her; Lu, Wei Yi; Lin, Chu Chieh; Datta, Amitabha; Huang, Jui-Hsien.

In: Journal of Organometallic Chemistry, Vol. 791, 12.06.2015, p. 141-147.

Research output: Contribution to journalArticle

TY - JOUR

T1 - New types of bi- and tri-dentate pyrrole-piperazine ligands and related zinc compounds

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

AU - Wu, Ming Chun

AU - Hu, Ting Chia

AU - Lo, Ya Chun

AU - Lee, Ting Yu

AU - Lin, Chia Her

AU - Lu, Wei Yi

AU - Lin, Chu Chieh

AU - Datta, Amitabha

AU - Huang, Jui-Hsien

PY - 2015/6/12

Y1 - 2015/6/12

N2 - Reactions of one or two equivalents of formaldehyde and phenylpiperazine with pyrrole in methanol or ethanol generated substituted pyrrole ligands C4H3NH-[2-CH2N(CH2CH2)2NPh] (1) and C4H2NH-{2,5-[CH2N(CH2CH2)2NPh]2} (2), respectively. Reacting 1 with one equivalent of ZnMe2 in toluene generated a di-zinc compound 3, {ZnMe{C4H3N-[2-CH2N(CH2CH2)2NPh]}}2, in moderate yield. Further reacting 3 with two equivalents of p-cresol in toluene overnight afforded pheoxide bridged di-zinc compound 4, {Zn(μ-O-C6H4-4-Me){C4H3N-[2-CH2N(CH2CH2)2NPh]}}2. Similarly, the reactions of one and two equivalents of tridentate substituted pyrrole ligand 2 with ZnMe2 afforded Zn compounds ZnMe{C4H2N-{2,5-[CH2N(CH2CH2)2NPh]2}} (5) and Zn{C4H2N-{2,5-[CH2N(CH2CH2)2NPh]2}}2 (6), respectively, in moderate yield. All of these compounds were characterized using 1H and 13C NMR spectroscopy. Compound 5 is relatively air and moisture sensitive and decomposes during the recrystallization process to yield a tri-Zn cluster, {Zn(μ2-OH){C4H2N-{2,5-[CH2N(CH2CH2)2NPh]2}}}3 (7). The molecular geometries of compounds 1, 3, 4, 6, and 7 were also determined using single crystal X-ray diffractometric analysis. Compounds 3, 4, and 6 were used as initiators for the ring opening polymerization of ε-caprolactone, and all of the zinc compounds showed high conversion with broad or bimodal molecular weight distributions.

AB - Reactions of one or two equivalents of formaldehyde and phenylpiperazine with pyrrole in methanol or ethanol generated substituted pyrrole ligands C4H3NH-[2-CH2N(CH2CH2)2NPh] (1) and C4H2NH-{2,5-[CH2N(CH2CH2)2NPh]2} (2), respectively. Reacting 1 with one equivalent of ZnMe2 in toluene generated a di-zinc compound 3, {ZnMe{C4H3N-[2-CH2N(CH2CH2)2NPh]}}2, in moderate yield. Further reacting 3 with two equivalents of p-cresol in toluene overnight afforded pheoxide bridged di-zinc compound 4, {Zn(μ-O-C6H4-4-Me){C4H3N-[2-CH2N(CH2CH2)2NPh]}}2. Similarly, the reactions of one and two equivalents of tridentate substituted pyrrole ligand 2 with ZnMe2 afforded Zn compounds ZnMe{C4H2N-{2,5-[CH2N(CH2CH2)2NPh]2}} (5) and Zn{C4H2N-{2,5-[CH2N(CH2CH2)2NPh]2}}2 (6), respectively, in moderate yield. All of these compounds were characterized using 1H and 13C NMR spectroscopy. Compound 5 is relatively air and moisture sensitive and decomposes during the recrystallization process to yield a tri-Zn cluster, {Zn(μ2-OH){C4H2N-{2,5-[CH2N(CH2CH2)2NPh]2}}}3 (7). The molecular geometries of compounds 1, 3, 4, 6, and 7 were also determined using single crystal X-ray diffractometric analysis. Compounds 3, 4, and 6 were used as initiators for the ring opening polymerization of ε-caprolactone, and all of the zinc compounds showed high conversion with broad or bimodal molecular weight distributions.

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JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

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