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

Helena Quilter, Rachel Drewitt, Mary Mahon, Gabriele Kociok-Kohn, Matthew Jones

Research output: Contribution to journal › Article

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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

Cite this

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. / Quilter, Helena; Drewitt, Rachel; Mahon, Mary; Kociok-Kohn, Gabriele; Jones, Matthew.

In: Journal of Organometallic Chemistry, Vol. 848, 15.10.2017, p. 325-331.

Research output: Contribution to journal › Article

Quilter, H, Drewitt, R, Mahon, M, Kociok-Kohn, G & Jones, M 2017, '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' Journal of Organometallic Chemistry, vol. 848, pp. 325-331. https://doi.org/10.1016/j.jorganchem.2017.08.014
Quilter H, Drewitt R, Mahon M, Kociok-Kohn G, Jones M. 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. Journal of Organometallic Chemistry. 2017 Oct 15;848:325-331. https://doi.org/10.1016/j.jorganchem.2017.08.014
Quilter, Helena ; Drewitt, Rachel ; Mahon, Mary ; Kociok-Kohn, Gabriele ; Jones, Matthew. / 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. In: Journal of Organometallic Chemistry. 2017 ; Vol. 848. pp. 325-331.
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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.",
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AU - Kociok-Kohn, Gabriele

AU - Jones, Matthew

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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.

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JO - Journal of Organometallic Chemistry

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SN - 0022-328X

ER -

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