Synthesis and structural studies of lithium and sodium complexes with OOO-tridentate bis(phenolate) ligands: Effective catalysts for the ring-opening polymerization of L-lactide

Yong Huang, Yueh Hsuan Tsai, Wen Chou Hung, Chieh Shen Lin, Wei Wang, Jui Hsien Huang, Saikat Dutta, Chu Chieh Lin

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Abstract

A series of lithium and sodium complexes with OOO-tridentate bis(phenolate) ligands have been synthesized and fully characterized. The reaction of 2,2'-dihydroxy-3,3',5,5'-tetrakis[(1-methyl-1-phenyl)ethyl]dibenzyl ether (L1-H2) with different ratios of nBuLi in toluene or tetrahydrofuran (THF) gave [Li2(L1-H) 2] (1), [Li4L12] (2), and [Li 2L1(THF)3] (3), respectively. Similarly, [Na(L1-H)(THF)] (4), [Na2(L1-H)]2 (5), and [Na4L12] (6) were prepared by the reaction of L1-H2 and NaN[Si(CH3) 3]2 or sodium metal. In addition, the reaction of 2,2'-dihydroxy-3,3',5,5'-tetra-tert-butyldibenzyl ether (L2-H 2) with nBuLi in toluene or THF yields Li 2(L2-H)2] (7) and [Li2(L 2-H)2(THF)2] (8), respectively. Further treatment of 7 with 2 mol equiv of benzyl alcohol provides [Li 2(L2-H)2(BnOH)2] (9). Complexes 1-4 and 6-9 have been structurally characterized by single-crystal X-ray analysis. The dinuclear nature of complexes 1 and 3 was confirmed from their molecular structure. Complexes 2 and 6 illustrate tetranuclear species; however, complex 4 shows a mononuclear feature. A p-π interaction exists from the phenyl ring of the 2-(methyl-1-phenylethyl) groups to the central metal in complexes 2, 4, and 6, which could effectively stabilize the metal center. Among them, complexes 1, 2, and 5-9 displayed efficient catalytic behavior for the ring-opening polymerization of L-lactide in the presence of benzyl alcohol. Experimental results indicate that among these alkali-metal complexes, the sodium compound 6 displays a rapid catalytic polymerization of L-lactide in "living" fashion, yielding poly(L-lactide) with a controlled molecular weight and narrow polydispersity indices for a wide range of monomer-to-initiator ratios.

Original languageEnglish
Pages (from-to)9416-9425
Number of pages10
JournalInorganic Chemistry
Volume49
Issue number20
DOIs
Publication statusPublished - 2010 Oct 18

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Ring opening polymerization
tetrahydrofuran
Lithium
polymerization
lithium
Sodium
sodium
Ligands
catalysts
ligands
Catalysts
rings
Benzyl Alcohol
synthesis
Metals
Toluene
toluene
ethers
alcohols
Sodium Compounds

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

Huang, Yong ; Tsai, Yueh Hsuan ; Hung, Wen Chou ; Lin, Chieh Shen ; Wang, Wei ; Huang, Jui Hsien ; Dutta, Saikat ; Lin, Chu Chieh. / Synthesis and structural studies of lithium and sodium complexes with OOO-tridentate bis(phenolate) ligands : Effective catalysts for the ring-opening polymerization of L-lactide. In: Inorganic Chemistry. 2010 ; Vol. 49, No. 20. pp. 9416-9425.
@article{31324740ee9547f4b2ff1b4b2cdfbd57,
title = "Synthesis and structural studies of lithium and sodium complexes with OOO-tridentate bis(phenolate) ligands: Effective catalysts for the ring-opening polymerization of L-lactide",
abstract = "A series of lithium and sodium complexes with OOO-tridentate bis(phenolate) ligands have been synthesized and fully characterized. The reaction of 2,2'-dihydroxy-3,3',5,5'-tetrakis[(1-methyl-1-phenyl)ethyl]dibenzyl ether (L1-H2) with different ratios of nBuLi in toluene or tetrahydrofuran (THF) gave [Li2(L1-H) 2] (1), [Li4L12] (2), and [Li 2L1(THF)3] (3), respectively. Similarly, [Na(L1-H)(THF)] (4), [Na2(L1-H)]2 (5), and [Na4L12] (6) were prepared by the reaction of L1-H2 and NaN[Si(CH3) 3]2 or sodium metal. In addition, the reaction of 2,2'-dihydroxy-3,3',5,5'-tetra-tert-butyldibenzyl ether (L2-H 2) with nBuLi in toluene or THF yields Li 2(L2-H)2] (7) and [Li2(L 2-H)2(THF)2] (8), respectively. Further treatment of 7 with 2 mol equiv of benzyl alcohol provides [Li 2(L2-H)2(BnOH)2] (9). Complexes 1-4 and 6-9 have been structurally characterized by single-crystal X-ray analysis. The dinuclear nature of complexes 1 and 3 was confirmed from their molecular structure. Complexes 2 and 6 illustrate tetranuclear species; however, complex 4 shows a mononuclear feature. A p-π interaction exists from the phenyl ring of the 2-(methyl-1-phenylethyl) groups to the central metal in complexes 2, 4, and 6, which could effectively stabilize the metal center. Among them, complexes 1, 2, and 5-9 displayed efficient catalytic behavior for the ring-opening polymerization of L-lactide in the presence of benzyl alcohol. Experimental results indicate that among these alkali-metal complexes, the sodium compound 6 displays a rapid catalytic polymerization of L-lactide in {"}living{"} fashion, yielding poly(L-lactide) with a controlled molecular weight and narrow polydispersity indices for a wide range of monomer-to-initiator ratios.",
author = "Yong Huang and Tsai, {Yueh Hsuan} and Hung, {Wen Chou} and Lin, {Chieh Shen} and Wei Wang and Huang, {Jui Hsien} and Saikat Dutta and Lin, {Chu Chieh}",
year = "2010",
month = "10",
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volume = "49",
pages = "9416--9425",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
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Synthesis and structural studies of lithium and sodium complexes with OOO-tridentate bis(phenolate) ligands : Effective catalysts for the ring-opening polymerization of L-lactide. / Huang, Yong; Tsai, Yueh Hsuan; Hung, Wen Chou; Lin, Chieh Shen; Wang, Wei; Huang, Jui Hsien; Dutta, Saikat; Lin, Chu Chieh.

In: Inorganic Chemistry, Vol. 49, No. 20, 18.10.2010, p. 9416-9425.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Synthesis and structural studies of lithium and sodium complexes with OOO-tridentate bis(phenolate) ligands

T2 - Effective catalysts for the ring-opening polymerization of L-lactide

AU - Huang, Yong

AU - Tsai, Yueh Hsuan

AU - Hung, Wen Chou

AU - Lin, Chieh Shen

AU - Wang, Wei

AU - Huang, Jui Hsien

AU - Dutta, Saikat

AU - Lin, Chu Chieh

PY - 2010/10/18

Y1 - 2010/10/18

N2 - A series of lithium and sodium complexes with OOO-tridentate bis(phenolate) ligands have been synthesized and fully characterized. The reaction of 2,2'-dihydroxy-3,3',5,5'-tetrakis[(1-methyl-1-phenyl)ethyl]dibenzyl ether (L1-H2) with different ratios of nBuLi in toluene or tetrahydrofuran (THF) gave [Li2(L1-H) 2] (1), [Li4L12] (2), and [Li 2L1(THF)3] (3), respectively. Similarly, [Na(L1-H)(THF)] (4), [Na2(L1-H)]2 (5), and [Na4L12] (6) were prepared by the reaction of L1-H2 and NaN[Si(CH3) 3]2 or sodium metal. In addition, the reaction of 2,2'-dihydroxy-3,3',5,5'-tetra-tert-butyldibenzyl ether (L2-H 2) with nBuLi in toluene or THF yields Li 2(L2-H)2] (7) and [Li2(L 2-H)2(THF)2] (8), respectively. Further treatment of 7 with 2 mol equiv of benzyl alcohol provides [Li 2(L2-H)2(BnOH)2] (9). Complexes 1-4 and 6-9 have been structurally characterized by single-crystal X-ray analysis. The dinuclear nature of complexes 1 and 3 was confirmed from their molecular structure. Complexes 2 and 6 illustrate tetranuclear species; however, complex 4 shows a mononuclear feature. A p-π interaction exists from the phenyl ring of the 2-(methyl-1-phenylethyl) groups to the central metal in complexes 2, 4, and 6, which could effectively stabilize the metal center. Among them, complexes 1, 2, and 5-9 displayed efficient catalytic behavior for the ring-opening polymerization of L-lactide in the presence of benzyl alcohol. Experimental results indicate that among these alkali-metal complexes, the sodium compound 6 displays a rapid catalytic polymerization of L-lactide in "living" fashion, yielding poly(L-lactide) with a controlled molecular weight and narrow polydispersity indices for a wide range of monomer-to-initiator ratios.

AB - A series of lithium and sodium complexes with OOO-tridentate bis(phenolate) ligands have been synthesized and fully characterized. The reaction of 2,2'-dihydroxy-3,3',5,5'-tetrakis[(1-methyl-1-phenyl)ethyl]dibenzyl ether (L1-H2) with different ratios of nBuLi in toluene or tetrahydrofuran (THF) gave [Li2(L1-H) 2] (1), [Li4L12] (2), and [Li 2L1(THF)3] (3), respectively. Similarly, [Na(L1-H)(THF)] (4), [Na2(L1-H)]2 (5), and [Na4L12] (6) were prepared by the reaction of L1-H2 and NaN[Si(CH3) 3]2 or sodium metal. In addition, the reaction of 2,2'-dihydroxy-3,3',5,5'-tetra-tert-butyldibenzyl ether (L2-H 2) with nBuLi in toluene or THF yields Li 2(L2-H)2] (7) and [Li2(L 2-H)2(THF)2] (8), respectively. Further treatment of 7 with 2 mol equiv of benzyl alcohol provides [Li 2(L2-H)2(BnOH)2] (9). Complexes 1-4 and 6-9 have been structurally characterized by single-crystal X-ray analysis. The dinuclear nature of complexes 1 and 3 was confirmed from their molecular structure. Complexes 2 and 6 illustrate tetranuclear species; however, complex 4 shows a mononuclear feature. A p-π interaction exists from the phenyl ring of the 2-(methyl-1-phenylethyl) groups to the central metal in complexes 2, 4, and 6, which could effectively stabilize the metal center. Among them, complexes 1, 2, and 5-9 displayed efficient catalytic behavior for the ring-opening polymerization of L-lactide in the presence of benzyl alcohol. Experimental results indicate that among these alkali-metal complexes, the sodium compound 6 displays a rapid catalytic polymerization of L-lactide in "living" fashion, yielding poly(L-lactide) with a controlled molecular weight and narrow polydispersity indices for a wide range of monomer-to-initiator ratios.

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