Synthesis of Li(I), Zn(II) and Mg(II) complexes of amine bis(phenolates) and their exploitation for the ring opening polymerisation of rac-lactide

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Abstract

In this paper a series of Mg(II), Li(I) and Zn(II) complexes based on two families of amine bis(phenolate)s have been prepared and structurally characterised. In the solid-state the Li(I) complexes form common Li4O4 cubes and there are subtle differences in coordination mode between the two salan ligands employed. We also have prepared a Li3Mg1O4 cube structure, by the reaction of 1 eq. of ligand 2H2, with 1 eq. of both nBuLi and MgnBu2. Upon addition of the ligands with Zn(II) either a trimetallic or tetrametallic structure was isolated. With 2H2 a complex with an –OMe was observed, this arises from the insertion of oxygen into the Zn-Me bond. Upon reaction with MgnBu2 dimeric complexes were isolated. All complexes were tested for the ROP of rac-lactide in solution. High molecular weight polylactide was isolated with narrow molecular weight distributions being observed. In most cases PLA with a very slight heterotactic bias was formed.
LanguageEnglish
Pages325-331
JournalJournal of Organometallic Chemistry
Volume848
Early online date24 Aug 2017
DOIs
StatusPublished - 15 Oct 2017

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Ring opening polymerization
exploitation
Polymerization
Amines
amines
polymerization
Ligands
ligands
rings
molecular weight
synthesis
Molecular Weight
Molecular weight distribution
insertion
Molecular weight
Oxygen
solid state
oxygen
dilactide

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title = "Synthesis of Li(I), Zn(II) and Mg(II) complexes of amine bis(phenolates) and their exploitation for the ring opening polymerisation of rac-lactide",
abstract = "In this paper a series of Mg(II), Li(I) and Zn(II) complexes based on two families of amine bis(phenolate)s have been prepared and structurally characterised. In the solid-state the Li(I) complexes form common Li4O4 cubes and there are subtle differences in coordination mode between the two salan ligands employed. We also have prepared a Li3Mg1O4 cube structure, by the reaction of 1 eq. of ligand 2H2, with 1 eq. of both nBuLi and MgnBu2. Upon addition of the ligands with Zn(II) either a trimetallic or tetrametallic structure was isolated. With 2H2 a complex with an –OMe was observed, this arises from the insertion of oxygen into the Zn-Me bond. Upon reaction with MgnBu2 dimeric complexes were isolated. All complexes were tested for the ROP of rac-lactide in solution. High molecular weight polylactide was isolated with narrow molecular weight distributions being observed. In most cases PLA with a very slight heterotactic bias was formed.",
author = "Helena Quilter and Rachel Drewitt and Mary Mahon and Gabriele Kociok-Kohn and Matthew Jones",
year = "2017",
month = "10",
day = "15",
doi = "10.1016/j.jorganchem.2017.08.014",
language = "English",
volume = "848",
pages = "325--331",
journal = "Journal of Organometallic Chemistry",
issn = "0022-328X",
publisher = "Elsevier",

}

TY - JOUR

T1 - Synthesis of Li(I), Zn(II) and Mg(II) complexes of amine bis(phenolates) and their exploitation for the ring opening polymerisation of rac-lactide

AU - Quilter,Helena

AU - Drewitt,Rachel

AU - Mahon,Mary

AU - Kociok-Kohn,Gabriele

AU - Jones,Matthew

PY - 2017/10/15

Y1 - 2017/10/15

N2 - In this paper a series of Mg(II), Li(I) and Zn(II) complexes based on two families of amine bis(phenolate)s have been prepared and structurally characterised. In the solid-state the Li(I) complexes form common Li4O4 cubes and there are subtle differences in coordination mode between the two salan ligands employed. We also have prepared a Li3Mg1O4 cube structure, by the reaction of 1 eq. of ligand 2H2, with 1 eq. of both nBuLi and MgnBu2. Upon addition of the ligands with Zn(II) either a trimetallic or tetrametallic structure was isolated. With 2H2 a complex with an –OMe was observed, this arises from the insertion of oxygen into the Zn-Me bond. Upon reaction with MgnBu2 dimeric complexes were isolated. All complexes were tested for the ROP of rac-lactide in solution. High molecular weight polylactide was isolated with narrow molecular weight distributions being observed. In most cases PLA with a very slight heterotactic bias was formed.

AB - In this paper a series of Mg(II), Li(I) and Zn(II) complexes based on two families of amine bis(phenolate)s have been prepared and structurally characterised. In the solid-state the Li(I) complexes form common Li4O4 cubes and there are subtle differences in coordination mode between the two salan ligands employed. We also have prepared a Li3Mg1O4 cube structure, by the reaction of 1 eq. of ligand 2H2, with 1 eq. of both nBuLi and MgnBu2. Upon addition of the ligands with Zn(II) either a trimetallic or tetrametallic structure was isolated. With 2H2 a complex with an –OMe was observed, this arises from the insertion of oxygen into the Zn-Me bond. Upon reaction with MgnBu2 dimeric complexes were isolated. All complexes were tested for the ROP of rac-lactide in solution. High molecular weight polylactide was isolated with narrow molecular weight distributions being observed. In most cases PLA with a very slight heterotactic bias was formed.

UR - https://doi.org/10.1016/j.jorganchem.2017.08.014

U2 - 10.1016/j.jorganchem.2017.08.014

DO - 10.1016/j.jorganchem.2017.08.014

M3 - Article

VL - 848

SP - 325

EP - 331

JO - Journal of Organometallic Chemistry

T2 - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

SN - 0022-328X

ER -