Mono-aluminum, di-magnesium and tri-zinc complexes supported by bisphenolate ligand: Synthesis, characterization and catalytic studies for ring-opening polymerization of cyclic esters

Chen Yu Li; Po Sheng Chen; Shi Jie Hsu; Chia Her Lin; Hsi Ya Huang; Bao Tsan Ko

doi:10.1016/j.jorganchem.2012.06.019

Mono-aluminum, di-magnesium and tri-zinc complexes supported by bisphenolate ligand: Synthesis, characterization and catalytic studies for ring-opening polymerization of cyclic esters

Chen Yu Li, Po Sheng Chen, Shi Jie Hsu, Chia Her Lin, Hsi Ya Huang, Bao Tsan Ko^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

17 Citations (Scopus)

Abstract

Mono-aluminum, di-magnesium and tri-zinc complexes coordinated by a Biphen ^2- ligand (Biphen-H ₂ = 3,3′-di-tert-butyl-5, 5′,6,6′-tetramethylbiphenyl-2,2′-diol) were synthesized and structurally characterized by X-ray single crystal determinations. The reaction of Biphen-H ₂ with AlMe3 (1.0 mol equiv.) in THF produced the tetra-coordinated monomeric aluminum complex [Al(Biphen)Me(THF)] (1), but treatment of Biphen-H ₂ with Mg ⁿBu ₂ under the same stoichiometric proportion in THF gave the dimeric magnesium complex [Mg(μ-Biphen)(THF)] ₂ (2). Tri-zinc [Zn ₃(μ, μ-Biphen) ₂Et ₂(THF) ₂] (3) resulted from treatment of Biphen-H ₂ with ZnEt ₂ (1.5 mol equiv) in THF; it consists of two different kinds of four-coordinated Zn centers. All of metal complexes are coordinated by at least one neutral THF coligand, indicating each metal center can behave as an active site to activate monomers during ring-opening polymerization (ROP). Catalysis for ROP of ε-caprolactone (ε-CL) or β-butyrolactone (β-BL) of complexes 1-3 are investigated, and the comparative studies of ε-CL polymerization are also discussed.

Original language	English
Pages (from-to)	175-181
Number of pages	7
Journal	Journal of Organometallic Chemistry
Volume	716
DOIs	https://doi.org/10.1016/j.jorganchem.2012.06.019
Publication status	Published - 2012 Oct 1
Externally published	Yes

Keywords

Bisphenolate
Catalyst
Ring-opening polymerization
Zinc
β-Butyrolactone
ε-Caprolactone

ASJC Scopus subject areas

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry
Materials Chemistry

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10.1016/j.jorganchem.2012.06.019

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Mono-aluminum, di-magnesium and tri-zinc complexes supported by bisphenolate ligand: Synthesis, characterization and catalytic studies for ring-opening polymerization of cyclic esters. / Li, Chen Yu; Chen, Po Sheng; Hsu, Shi Jie et al.
In: Journal of Organometallic Chemistry, Vol. 716, 01.10.2012, p. 175-181.

Research output: Contribution to journal › Article › peer-review

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title = "Mono-aluminum, di-magnesium and tri-zinc complexes supported by bisphenolate ligand: Synthesis, characterization and catalytic studies for ring-opening polymerization of cyclic esters",

abstract = "Mono-aluminum, di-magnesium and tri-zinc complexes coordinated by a Biphen 2- ligand (Biphen-H 2 = 3,3′-di-tert-butyl-5, 5′,6,6′-tetramethylbiphenyl-2,2′-diol) were synthesized and structurally characterized by X-ray single crystal determinations. The reaction of Biphen-H 2 with AlMe3 (1.0 mol equiv.) in THF produced the tetra-coordinated monomeric aluminum complex [Al(Biphen)Me(THF)] (1), but treatment of Biphen-H 2 with Mg nBu 2 under the same stoichiometric proportion in THF gave the dimeric magnesium complex [Mg(μ-Biphen)(THF)] 2 (2). Tri-zinc [Zn 3(μ, μ-Biphen) 2Et 2(THF) 2] (3) resulted from treatment of Biphen-H 2 with ZnEt 2 (1.5 mol equiv) in THF; it consists of two different kinds of four-coordinated Zn centers. All of metal complexes are coordinated by at least one neutral THF coligand, indicating each metal center can behave as an active site to activate monomers during ring-opening polymerization (ROP). Catalysis for ROP of ε-caprolactone (ε-CL) or β-butyrolactone (β-BL) of complexes 1-3 are investigated, and the comparative studies of ε-CL polymerization are also discussed.",

keywords = "Bisphenolate, Catalyst, Ring-opening polymerization, Zinc, β-Butyrolactone, ε-Caprolactone",

author = "Li, {Chen Yu} and Chen, {Po Sheng} and Hsu, {Shi Jie} and Lin, {Chia Her} and Huang, {Hsi Ya} and Ko, {Bao Tsan}",

note = "Funding Information: We gratefully acknowledge the financial support from the National Science Council, Taiwan ( NSC99-2113-M-033-007-MY2 to B.-T. Ko and NSC100- 2632-M-033-001-MY3 to H.-Y. Huang). We also thank Professor Chu-Chieh Lin for valuable discussions. ",

year = "2012",

month = oct,

day = "1",

doi = "10.1016/j.jorganchem.2012.06.019",

language = "English",

volume = "716",

pages = "175--181",

journal = "Journal of Organometallic Chemistry",

issn = "0022-328X",

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T1 - Mono-aluminum, di-magnesium and tri-zinc complexes supported by bisphenolate ligand

T2 - Synthesis, characterization and catalytic studies for ring-opening polymerization of cyclic esters

AU - Li, Chen Yu

AU - Chen, Po Sheng

AU - Hsu, Shi Jie

AU - Lin, Chia Her

AU - Huang, Hsi Ya

AU - Ko, Bao Tsan

N1 - Funding Information: We gratefully acknowledge the financial support from the National Science Council, Taiwan ( NSC99-2113-M-033-007-MY2 to B.-T. Ko and NSC100- 2632-M-033-001-MY3 to H.-Y. Huang). We also thank Professor Chu-Chieh Lin for valuable discussions.

PY - 2012/10/1

Y1 - 2012/10/1

N2 - Mono-aluminum, di-magnesium and tri-zinc complexes coordinated by a Biphen 2- ligand (Biphen-H 2 = 3,3′-di-tert-butyl-5, 5′,6,6′-tetramethylbiphenyl-2,2′-diol) were synthesized and structurally characterized by X-ray single crystal determinations. The reaction of Biphen-H 2 with AlMe3 (1.0 mol equiv.) in THF produced the tetra-coordinated monomeric aluminum complex [Al(Biphen)Me(THF)] (1), but treatment of Biphen-H 2 with Mg nBu 2 under the same stoichiometric proportion in THF gave the dimeric magnesium complex [Mg(μ-Biphen)(THF)] 2 (2). Tri-zinc [Zn 3(μ, μ-Biphen) 2Et 2(THF) 2] (3) resulted from treatment of Biphen-H 2 with ZnEt 2 (1.5 mol equiv) in THF; it consists of two different kinds of four-coordinated Zn centers. All of metal complexes are coordinated by at least one neutral THF coligand, indicating each metal center can behave as an active site to activate monomers during ring-opening polymerization (ROP). Catalysis for ROP of ε-caprolactone (ε-CL) or β-butyrolactone (β-BL) of complexes 1-3 are investigated, and the comparative studies of ε-CL polymerization are also discussed.

AB - Mono-aluminum, di-magnesium and tri-zinc complexes coordinated by a Biphen 2- ligand (Biphen-H 2 = 3,3′-di-tert-butyl-5, 5′,6,6′-tetramethylbiphenyl-2,2′-diol) were synthesized and structurally characterized by X-ray single crystal determinations. The reaction of Biphen-H 2 with AlMe3 (1.0 mol equiv.) in THF produced the tetra-coordinated monomeric aluminum complex [Al(Biphen)Me(THF)] (1), but treatment of Biphen-H 2 with Mg nBu 2 under the same stoichiometric proportion in THF gave the dimeric magnesium complex [Mg(μ-Biphen)(THF)] 2 (2). Tri-zinc [Zn 3(μ, μ-Biphen) 2Et 2(THF) 2] (3) resulted from treatment of Biphen-H 2 with ZnEt 2 (1.5 mol equiv) in THF; it consists of two different kinds of four-coordinated Zn centers. All of metal complexes are coordinated by at least one neutral THF coligand, indicating each metal center can behave as an active site to activate monomers during ring-opening polymerization (ROP). Catalysis for ROP of ε-caprolactone (ε-CL) or β-butyrolactone (β-BL) of complexes 1-3 are investigated, and the comparative studies of ε-CL polymerization are also discussed.

KW - Bisphenolate

KW - Catalyst

KW - Ring-opening polymerization

KW - Zinc

KW - β-Butyrolactone

KW - ε-Caprolactone

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U2 - 10.1016/j.jorganchem.2012.06.019

DO - 10.1016/j.jorganchem.2012.06.019

M3 - Article

AN - SCOPUS:84864977283

SN - 0022-328X

VL - 716

SP - 175

EP - 181

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

ER -

Mono-aluminum, di-magnesium and tri-zinc complexes supported by bisphenolate ligand: Synthesis, characterization and catalytic studies for ring-opening polymerization of cyclic esters

Abstract

Keywords

ASJC Scopus subject areas

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