Copper(II) complexes containing N,N′-bidentate N-substituted N-(pyridin-2-ylmethyl)amine: Synthesis, structure and application towards polymerization of rac-lactide

Seoung Hyun Ahn; Min Kyung Chun; Eunhee Kim; Jong Hwa Jeong; Saira Nayab; Hyosun Lee

doi:10.1016/j.poly.2017.01.050

Copper(II) complexes containing N,N′-bidentate N-substituted N-(pyridin-2-ylmethyl)amine: Synthesis, structure and application towards polymerization of rac-lactide

Seoung Hyun Ahn, Min Kyung Chun, Eunhee Kim, Jong Hwa Jeong, Saira Nayab, Hyosun Lee

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Abstract

The reaction between [CuCl₂·2H₂O] and N,N′-bidentate N-(pyridin-2-ylmethyl)amines (L_n= L_A–L_E) in methanol yielded new Cu(II) complexes; namely mononuclear [L_ACuCl₂] and dinuclear [L_nCu(μ-Cl)Cl]₂(L_n= L_B–L_E) complexes, respectively. Monomeric [L_ACuCl₂] showed a distorted square planar geometry around copper metal based on X-ray crystallography. The dimeric [L_nCu(μ-Cl)Cl]₂(L_n= L_B–L_E) had a chloro-bridged 5-coordinated and a distorted square pyramidal geometry around the Cu(II) center. The range of Cu⋯Cu′ distance was 3.3238(6)–3.593(2) Å in [L_nCu(μ-Cl)Cl]₂(L_n= L_B–L_E). The Cu(II)-alkoxy derivatives, generated in situ, of these synthesized Cu(II) complexes have shown moderate activity towards the polymerization of rac-lactide (rac-LA) and yielded hetero-enriched PLA. The steric hindrance and electronic effects has a great influence on the catalytic activity and stereoselectivity of initiators.

Original language	English
Pages (from-to)	51-58
Number of pages	8
Journal	Polyhedron
Volume	127
DOIs	https://doi.org/10.1016/j.poly.2017.01.050
State	Published - 2017

Keywords

Dinuclear copper(II) complex
Heterotacticity
Molecular structure
Rac-lactide
Ring opening polymerization

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@article{bd05129c25fd47edbbcce77a20403df9,

title = "Copper(II) complexes containing N,N′-bidentate N-substituted N-(pyridin-2-ylmethyl)amine: Synthesis, structure and application towards polymerization of rac-lactide",

abstract = "The reaction between [CuCl2·2H2O] and N,N′-bidentate N-(pyridin-2-ylmethyl)amines (Ln= LA–LE) in methanol yielded new Cu(II) complexes; namely mononuclear [LACuCl2] and dinuclear [LnCu(μ-Cl)Cl]2(Ln= LB–LE) complexes, respectively. Monomeric [LACuCl2] showed a distorted square planar geometry around copper metal based on X-ray crystallography. The dimeric [LnCu(μ-Cl)Cl]2(Ln= LB–LE) had a chloro-bridged 5-coordinated and a distorted square pyramidal geometry around the Cu(II) center. The range of Cu⋯Cu′ distance was 3.3238(6)–3.593(2) {\AA} in [LnCu(μ-Cl)Cl]2(Ln= LB–LE). The Cu(II)-alkoxy derivatives, generated in situ, of these synthesized Cu(II) complexes have shown moderate activity towards the polymerization of rac-lactide (rac-LA) and yielded hetero-enriched PLA. The steric hindrance and electronic effects has a great influence on the catalytic activity and stereoselectivity of initiators.",

keywords = "Dinuclear copper(II) complex, Heterotacticity, Molecular structure, Rac-lactide, Ring opening polymerization",

author = "Ahn, {Seoung Hyun} and Chun, {Min Kyung} and Eunhee Kim and Jeong, {Jong Hwa} and Saira Nayab and Hyosun Lee",

note = "Publisher Copyright: {\textcopyright} 2017 Elsevier Ltd",

year = "2017",

doi = "10.1016/j.poly.2017.01.050",

language = "English",

volume = "127",

pages = "51--58",

journal = "Polyhedron",

issn = "0277-5387",

publisher = "Elsevier Ltd.",

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TY - JOUR

T1 - Copper(II) complexes containing N,N′-bidentate N-substituted N-(pyridin-2-ylmethyl)amine

T2 - Synthesis, structure and application towards polymerization of rac-lactide

AU - Ahn, Seoung Hyun

AU - Chun, Min Kyung

AU - Kim, Eunhee

AU - Jeong, Jong Hwa

AU - Nayab, Saira

AU - Lee, Hyosun

PY - 2017

Y1 - 2017

N2 - The reaction between [CuCl2·2H2O] and N,N′-bidentate N-(pyridin-2-ylmethyl)amines (Ln= LA–LE) in methanol yielded new Cu(II) complexes; namely mononuclear [LACuCl2] and dinuclear [LnCu(μ-Cl)Cl]2(Ln= LB–LE) complexes, respectively. Monomeric [LACuCl2] showed a distorted square planar geometry around copper metal based on X-ray crystallography. The dimeric [LnCu(μ-Cl)Cl]2(Ln= LB–LE) had a chloro-bridged 5-coordinated and a distorted square pyramidal geometry around the Cu(II) center. The range of Cu⋯Cu′ distance was 3.3238(6)–3.593(2) Å in [LnCu(μ-Cl)Cl]2(Ln= LB–LE). The Cu(II)-alkoxy derivatives, generated in situ, of these synthesized Cu(II) complexes have shown moderate activity towards the polymerization of rac-lactide (rac-LA) and yielded hetero-enriched PLA. The steric hindrance and electronic effects has a great influence on the catalytic activity and stereoselectivity of initiators.

AB - The reaction between [CuCl2·2H2O] and N,N′-bidentate N-(pyridin-2-ylmethyl)amines (Ln= LA–LE) in methanol yielded new Cu(II) complexes; namely mononuclear [LACuCl2] and dinuclear [LnCu(μ-Cl)Cl]2(Ln= LB–LE) complexes, respectively. Monomeric [LACuCl2] showed a distorted square planar geometry around copper metal based on X-ray crystallography. The dimeric [LnCu(μ-Cl)Cl]2(Ln= LB–LE) had a chloro-bridged 5-coordinated and a distorted square pyramidal geometry around the Cu(II) center. The range of Cu⋯Cu′ distance was 3.3238(6)–3.593(2) Å in [LnCu(μ-Cl)Cl]2(Ln= LB–LE). The Cu(II)-alkoxy derivatives, generated in situ, of these synthesized Cu(II) complexes have shown moderate activity towards the polymerization of rac-lactide (rac-LA) and yielded hetero-enriched PLA. The steric hindrance and electronic effects has a great influence on the catalytic activity and stereoselectivity of initiators.

KW - Dinuclear copper(II) complex

KW - Heterotacticity

KW - Molecular structure

KW - Rac-lactide

KW - Ring opening polymerization

UR - http://www.scopus.com/inward/record.url?scp=85013658003&partnerID=8YFLogxK

U2 - 10.1016/j.poly.2017.01.050

DO - 10.1016/j.poly.2017.01.050

M3 - Article

AN - SCOPUS:85013658003

SN - 0277-5387

VL - 127

SP - 51

EP - 58

JO - Polyhedron

JF - Polyhedron

ER -

Copper(II) complexes containing N,N′-bidentate N-substituted N-(pyridin-2-ylmethyl)amine: Synthesis, structure and application towards polymerization of rac-lactide

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