Metal influence on the iso- and hetero-selectivity of complexes of bipyrrolidine derived Salan ligands for the polymerisation of rac-lactide

Matthew Jones, Lauren Brady, Paul M Mckeown, Antoine Buchard, Pascal M Schafer, Lynne H Thomas, Mary F Mahon, Timothy J Woodman, John P Lowe

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Abstract

In this paper we have prepared a series of Ti(IV), Hf(IV) and Al(III) complexes based on bipyrrolidine salan pro-ligands. The Hf(IV) complexes have all been characterised in the solid-state, the chiral ligands coordinate to Hf(IV) in an α-cis manner whereas the meso ligand coordinates in a β-cis geometry. The Hf(IV) complexes are all active for the ROP of rac-lactide in the melt, with the fluxional meso complex affording a strong isotactic bias Pm = 0.84. As expected Hf(3)(OiPr)2 polymerised L-LA faster than rac-LA (kapp = 5.9 x 10-3 mins-1 vs 3.8 x 10-3 mins-1). For Ti(IV) complexes atactic PLA was formed. The salan pro-ligands have also been complexed to Al(III), with the complexes being characterised in the solid and solution state generating a series of novel Al-Me and Al-OiPr species. Al(1)(OiPr) was fluxional on the NMR timescale, whereas Al(3)(OiPr) was locked in solution with no exchange. Interestingly, the Al(III) complexes of 3H2 produce PLA with a very strong heterotactic bias Pr upto 0.87, whereas atactic PLA is produced with 1H2. For Al(3)(OiPr) a linear relationship is observed with Mn and conversion. Experiments with the addition of an equivalent of rac-LA to the selective initiators have also been performed and are discussed.
Original languageEnglish
Pages (from-to)5034-5039
Number of pages6
JournalChemical Science
Volume6
Issue number8
Early online date17 Jun 2015
DOIs
Publication statusPublished - 1 Aug 2015

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Metals
Polymerization
Ligands
Ion exchange
Nuclear magnetic resonance
Geometry
dilactide
Experiments

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title = "Metal influence on the iso- and hetero-selectivity of complexes of bipyrrolidine derived Salan ligands for the polymerisation of rac-lactide",
abstract = "In this paper we have prepared a series of Ti(IV), Hf(IV) and Al(III) complexes based on bipyrrolidine salan pro-ligands. The Hf(IV) complexes have all been characterised in the solid-state, the chiral ligands coordinate to Hf(IV) in an α-cis manner whereas the meso ligand coordinates in a β-cis geometry. The Hf(IV) complexes are all active for the ROP of rac-lactide in the melt, with the fluxional meso complex affording a strong isotactic bias Pm = 0.84. As expected Hf(3)(OiPr)2 polymerised L-LA faster than rac-LA (kapp = 5.9 x 10-3 mins-1 vs 3.8 x 10-3 mins-1). For Ti(IV) complexes atactic PLA was formed. The salan pro-ligands have also been complexed to Al(III), with the complexes being characterised in the solid and solution state generating a series of novel Al-Me and Al-OiPr species. Al(1)(OiPr) was fluxional on the NMR timescale, whereas Al(3)(OiPr) was locked in solution with no exchange. Interestingly, the Al(III) complexes of 3H2 produce PLA with a very strong heterotactic bias Pr upto 0.87, whereas atactic PLA is produced with 1H2. For Al(3)(OiPr) a linear relationship is observed with Mn and conversion. Experiments with the addition of an equivalent of rac-LA to the selective initiators have also been performed and are discussed.",
author = "Matthew Jones and Lauren Brady and Mckeown, {Paul M} and Antoine Buchard and Schafer, {Pascal M} and Thomas, {Lynne H} and Mahon, {Mary F} and Woodman, {Timothy J} and Lowe, {John P}",
year = "2015",
month = "8",
day = "1",
doi = "10.1039/C5SC01819F",
language = "English",
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journal = "Chemical Science",
issn = "2041-6520",
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TY - JOUR

T1 - Metal influence on the iso- and hetero-selectivity of complexes of bipyrrolidine derived Salan ligands for the polymerisation of rac-lactide

AU - Jones, Matthew

AU - Brady, Lauren

AU - Mckeown, Paul M

AU - Buchard, Antoine

AU - Schafer, Pascal M

AU - Thomas, Lynne H

AU - Mahon, Mary F

AU - Woodman, Timothy J

AU - Lowe, John P

PY - 2015/8/1

Y1 - 2015/8/1

N2 - In this paper we have prepared a series of Ti(IV), Hf(IV) and Al(III) complexes based on bipyrrolidine salan pro-ligands. The Hf(IV) complexes have all been characterised in the solid-state, the chiral ligands coordinate to Hf(IV) in an α-cis manner whereas the meso ligand coordinates in a β-cis geometry. The Hf(IV) complexes are all active for the ROP of rac-lactide in the melt, with the fluxional meso complex affording a strong isotactic bias Pm = 0.84. As expected Hf(3)(OiPr)2 polymerised L-LA faster than rac-LA (kapp = 5.9 x 10-3 mins-1 vs 3.8 x 10-3 mins-1). For Ti(IV) complexes atactic PLA was formed. The salan pro-ligands have also been complexed to Al(III), with the complexes being characterised in the solid and solution state generating a series of novel Al-Me and Al-OiPr species. Al(1)(OiPr) was fluxional on the NMR timescale, whereas Al(3)(OiPr) was locked in solution with no exchange. Interestingly, the Al(III) complexes of 3H2 produce PLA with a very strong heterotactic bias Pr upto 0.87, whereas atactic PLA is produced with 1H2. For Al(3)(OiPr) a linear relationship is observed with Mn and conversion. Experiments with the addition of an equivalent of rac-LA to the selective initiators have also been performed and are discussed.

AB - In this paper we have prepared a series of Ti(IV), Hf(IV) and Al(III) complexes based on bipyrrolidine salan pro-ligands. The Hf(IV) complexes have all been characterised in the solid-state, the chiral ligands coordinate to Hf(IV) in an α-cis manner whereas the meso ligand coordinates in a β-cis geometry. The Hf(IV) complexes are all active for the ROP of rac-lactide in the melt, with the fluxional meso complex affording a strong isotactic bias Pm = 0.84. As expected Hf(3)(OiPr)2 polymerised L-LA faster than rac-LA (kapp = 5.9 x 10-3 mins-1 vs 3.8 x 10-3 mins-1). For Ti(IV) complexes atactic PLA was formed. The salan pro-ligands have also been complexed to Al(III), with the complexes being characterised in the solid and solution state generating a series of novel Al-Me and Al-OiPr species. Al(1)(OiPr) was fluxional on the NMR timescale, whereas Al(3)(OiPr) was locked in solution with no exchange. Interestingly, the Al(III) complexes of 3H2 produce PLA with a very strong heterotactic bias Pr upto 0.87, whereas atactic PLA is produced with 1H2. For Al(3)(OiPr) a linear relationship is observed with Mn and conversion. Experiments with the addition of an equivalent of rac-LA to the selective initiators have also been performed and are discussed.

U2 - 10.1039/C5SC01819F

DO - 10.1039/C5SC01819F

M3 - Article

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JF - Chemical Science

SN - 2041-6520

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ER -