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Issue 27, 2018
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Bipyrrolidine salan alkoxide complexes of lanthanides: synthesis, characterisation, activity in the polymerisation of lactide and mechanistic investigation by DOSY NMR

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Abstract

Four dimeric lanthanide alkoxide complexes bearing ONNO bipyrrolidine salan ligands (LMeH2/LtBuH2) have been prepared with Nd, Sm and Yb. Depending on the metal and substituents, these complexes adopt varying coordination geometries. While investigating the hydrolytic degradation of these complexes, three dimeric mixed alkoxide/hydroxide and bis-hydroxide products were also prepared, isolated and characterised. Despite paramagnetism, 1H NMR and diffusion ordered spectroscopy (DOSY) allowed additional characterisation alongside elemental and single-crystal X-ray diffraction analyses. These systems were very active for the controlled ring-opening polymerisation (ROP) of rac-lactide (LA), under industrially relevant melt conditions and in solution, yielding complete conversion within 5 minutes at [Ln] : [LA] ratios of up to 3000 : 1 in toluene, and at 80 °C, whilst retaining low dispersities (Đ = 1.1). 1H DOSY NMR spectroscopy was employed to monitor polymer growth from the metal centres in situ, and revealed a dinuclear catalytically active species.

Graphical abstract: Bipyrrolidine salan alkoxide complexes of lanthanides: synthesis, characterisation, activity in the polymerisation of lactide and mechanistic investigation by DOSY NMR

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Publication details

The article was received on 23 May 2018, accepted on 18 Jun 2018 and first published on 19 Jun 2018


Article type: Paper
DOI: 10.1039/C8DT02108B
Citation: Dalton Trans., 2018,47, 9164-9172
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    Bipyrrolidine salan alkoxide complexes of lanthanides: synthesis, characterisation, activity in the polymerisation of lactide and mechanistic investigation by DOSY NMR

    J. Beament, G. Kociok-Köhn, M. D. Jones and A. Buchard, Dalton Trans., 2018, 47, 9164
    DOI: 10.1039/C8DT02108B

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