Zirconium and hafnium amide, alkoxide, and pyrrolyl complexes manifesting with pyrrolyl-linked N-donor ligands: Syntheses, characterization, and ring opening polymerization of ε-caprolactone

Wen Yi Lee, Chun Chin Hsieh, Jia Wei Hsu, Amitabha Datta, Yu Chun Lin, Jui-Hsien Huang, Ting Yu Lee

Research output: Contribution to journalArticle

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Abstract

A series of zirconium and hafnium alkoxide and amide complexes containing symmetrical tridentate pyrrolyl ligand, [C4H2NH(2,5- CH2NMe2)2] have been synthesized conveniently by treatment of 2,6-di-tert-butylphenol, tert-butanol or pyrrole in pentane and their reactivity over ring opening polymerization of ε-caprolactone have been carried out. Reactions of [C4H2NH(2,5-CH 2NMe2)2] with M(NEt2)4 (M = Zr or Hf) originate [C4H2N(2,5-CH2NMe 2)2]M(NEt2)3 (1, M = Zr; 2, M = Hf). Furthermore, reactions of [C4H2N(2,5-CH 2NMe2)2]M(NEt2)3 with 2,6-di-tert-butylphenol, tert-butanol or pyrrole afford [C4H 2N(2,5-CH2NMe2)2]M(OC 6H3-2,6-tBu2)(NEt2) 2 (3, M = Zr; 4, M = Hf), [C4H2N(2,5-CH 2NMe2)2]M(OtBu)3 (5, M = Zr; 6, M = Hf) and [C4H2N(2,5-CH2NMe 2)2]M(C4H4N)3 (7, M = Zr; 8, M = Hf), respectively, in satisfactory yield. All the complexes have been characterized by NMR spectra as well 3, 4 and 6 subjected to the X-ray diffraction analysis. Complexes 3-8 have been used as initiators for the ring-opening polymerization of ε-caprolactone and observed broad PDI values (1.84-2.75) representing multiple reactivity centers of these complexes.

Original languageEnglish
Pages (from-to)3816-3821
Number of pages6
JournalJournal of Organometallic Chemistry
Volume696
Issue number23
DOIs
Publication statusPublished - 2011 Nov 15

Fingerprint

Hafnium
tert-Butyl Alcohol
Pyrroles
hafnium
Ring opening polymerization
alkoxides
Butenes
Amides
Zirconium
Polymerization
amides
polymerization
Ligands
pyrroles
methylidyne
ligands
rings
synthesis
reactivity
X-Ray Diffraction

All Science Journal Classification (ASJC) codes

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

Cite this

@article{d87054aeefdf430b8ddd9e64a0c645f5,
title = "Zirconium and hafnium amide, alkoxide, and pyrrolyl complexes manifesting with pyrrolyl-linked N-donor ligands: Syntheses, characterization, and ring opening polymerization of ε-caprolactone",
abstract = "A series of zirconium and hafnium alkoxide and amide complexes containing symmetrical tridentate pyrrolyl ligand, [C4H2NH(2,5- CH2NMe2)2] have been synthesized conveniently by treatment of 2,6-di-tert-butylphenol, tert-butanol or pyrrole in pentane and their reactivity over ring opening polymerization of ε-caprolactone have been carried out. Reactions of [C4H2NH(2,5-CH 2NMe2)2] with M(NEt2)4 (M = Zr or Hf) originate [C4H2N(2,5-CH2NMe 2)2]M(NEt2)3 (1, M = Zr; 2, M = Hf). Furthermore, reactions of [C4H2N(2,5-CH 2NMe2)2]M(NEt2)3 with 2,6-di-tert-butylphenol, tert-butanol or pyrrole afford [C4H 2N(2,5-CH2NMe2)2]M(OC 6H3-2,6-tBu2)(NEt2) 2 (3, M = Zr; 4, M = Hf), [C4H2N(2,5-CH 2NMe2)2]M(OtBu)3 (5, M = Zr; 6, M = Hf) and [C4H2N(2,5-CH2NMe 2)2]M(C4H4N)3 (7, M = Zr; 8, M = Hf), respectively, in satisfactory yield. All the complexes have been characterized by NMR spectra as well 3, 4 and 6 subjected to the X-ray diffraction analysis. Complexes 3-8 have been used as initiators for the ring-opening polymerization of ε-caprolactone and observed broad PDI values (1.84-2.75) representing multiple reactivity centers of these complexes.",
author = "Lee, {Wen Yi} and Hsieh, {Chun Chin} and Hsu, {Jia Wei} and Amitabha Datta and Lin, {Yu Chun} and Jui-Hsien Huang and Lee, {Ting Yu}",
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language = "English",
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pages = "3816--3821",
journal = "Journal of Organometallic Chemistry",
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Zirconium and hafnium amide, alkoxide, and pyrrolyl complexes manifesting with pyrrolyl-linked N-donor ligands : Syntheses, characterization, and ring opening polymerization of ε-caprolactone. / Lee, Wen Yi; Hsieh, Chun Chin; Hsu, Jia Wei; Datta, Amitabha; Lin, Yu Chun; Huang, Jui-Hsien; Lee, Ting Yu.

In: Journal of Organometallic Chemistry, Vol. 696, No. 23, 15.11.2011, p. 3816-3821.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Zirconium and hafnium amide, alkoxide, and pyrrolyl complexes manifesting with pyrrolyl-linked N-donor ligands

T2 - Syntheses, characterization, and ring opening polymerization of ε-caprolactone

AU - Lee, Wen Yi

AU - Hsieh, Chun Chin

AU - Hsu, Jia Wei

AU - Datta, Amitabha

AU - Lin, Yu Chun

AU - Huang, Jui-Hsien

AU - Lee, Ting Yu

PY - 2011/11/15

Y1 - 2011/11/15

N2 - A series of zirconium and hafnium alkoxide and amide complexes containing symmetrical tridentate pyrrolyl ligand, [C4H2NH(2,5- CH2NMe2)2] have been synthesized conveniently by treatment of 2,6-di-tert-butylphenol, tert-butanol or pyrrole in pentane and their reactivity over ring opening polymerization of ε-caprolactone have been carried out. Reactions of [C4H2NH(2,5-CH 2NMe2)2] with M(NEt2)4 (M = Zr or Hf) originate [C4H2N(2,5-CH2NMe 2)2]M(NEt2)3 (1, M = Zr; 2, M = Hf). Furthermore, reactions of [C4H2N(2,5-CH 2NMe2)2]M(NEt2)3 with 2,6-di-tert-butylphenol, tert-butanol or pyrrole afford [C4H 2N(2,5-CH2NMe2)2]M(OC 6H3-2,6-tBu2)(NEt2) 2 (3, M = Zr; 4, M = Hf), [C4H2N(2,5-CH 2NMe2)2]M(OtBu)3 (5, M = Zr; 6, M = Hf) and [C4H2N(2,5-CH2NMe 2)2]M(C4H4N)3 (7, M = Zr; 8, M = Hf), respectively, in satisfactory yield. All the complexes have been characterized by NMR spectra as well 3, 4 and 6 subjected to the X-ray diffraction analysis. Complexes 3-8 have been used as initiators for the ring-opening polymerization of ε-caprolactone and observed broad PDI values (1.84-2.75) representing multiple reactivity centers of these complexes.

AB - A series of zirconium and hafnium alkoxide and amide complexes containing symmetrical tridentate pyrrolyl ligand, [C4H2NH(2,5- CH2NMe2)2] have been synthesized conveniently by treatment of 2,6-di-tert-butylphenol, tert-butanol or pyrrole in pentane and their reactivity over ring opening polymerization of ε-caprolactone have been carried out. Reactions of [C4H2NH(2,5-CH 2NMe2)2] with M(NEt2)4 (M = Zr or Hf) originate [C4H2N(2,5-CH2NMe 2)2]M(NEt2)3 (1, M = Zr; 2, M = Hf). Furthermore, reactions of [C4H2N(2,5-CH 2NMe2)2]M(NEt2)3 with 2,6-di-tert-butylphenol, tert-butanol or pyrrole afford [C4H 2N(2,5-CH2NMe2)2]M(OC 6H3-2,6-tBu2)(NEt2) 2 (3, M = Zr; 4, M = Hf), [C4H2N(2,5-CH 2NMe2)2]M(OtBu)3 (5, M = Zr; 6, M = Hf) and [C4H2N(2,5-CH2NMe 2)2]M(C4H4N)3 (7, M = Zr; 8, M = Hf), respectively, in satisfactory yield. All the complexes have been characterized by NMR spectra as well 3, 4 and 6 subjected to the X-ray diffraction analysis. Complexes 3-8 have been used as initiators for the ring-opening polymerization of ε-caprolactone and observed broad PDI values (1.84-2.75) representing multiple reactivity centers of these complexes.

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U2 - 10.1016/j.jorganchem.2011.09.001

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JF - Journal of Organometallic Chemistry

SN - 0022-328X

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