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Constrained geometry scandium permethylindenyl complexes for the ring-opening polymerisation of l- and rac-lactide.

Abstract:
The synthesis and characterisation of constrained geometry scandium permethylindenyl chloride, aryloxide and borohydride complexes Me2SB(tBuN,I*)Sc(Cl)(THF) (1), Me2SB(tBuN,I*)Sc(O-2,6-iPr-C6H3)(THF) (2), Me2SB(tBuN,I*)Sc(O-2,4-tBu-C6H3)(THF) (3) and Me2SB(tBuN,I*)Sc(BH4)(THF) (4) are reported. The activity of complexes 1-4 as initiators for the ring-opening polymerisation (ROP) of l- and rac-lactide is presented. The ROP of l- and rac-lactide using complexes 2 and 3 show first-order dependence on monomer concentration, and produced isotactic polylactide (PLA) and moderately heterotactic PLA (Pr = 0.68-0.72), respectively. Good agreement between experimental and theoretical molecular weights of PLA (Mn) and relatively narrow dispersities (Mw/Mn < 1.20) were obtained. Complex 4 showed higher activity for ROP of l- and rac-lactide than 2 or 3, with second-order dependence on monomer concentrations. However, poorly controlled molecular weights and lower heteroselectivity (Pr = 0.61-0.67) were observed. The effect of temperature and catalyst concentration for the ROP of l-lactide using 2 and 3 was also studied.
Publication status:
Published
Peer review status:
Peer reviewed

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Publisher copy:
10.1039/c9dt03450a

Authors


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Role:
Author
ORCID:
0000-0002-5859-357X
More by this author
Institution:
University of Oxford
Department:
Chemistry
Sub department:
Inorganic Chemistry
Role:
Author
ORCID:
0000-0003-2062-9546
More by this author
Institution:
University of Oxford
Department:
Chemistry
Sub department:
Inorganic Chemistry
Role:
Author
ORCID:
0000-0003-2044-9203
More by this author
Institution:
University of Oxford
Division:
MPLS
Department:
Chemistry
Sub department:
Inorganic Chemistry
Oxford college:
Balliol College
Role:
Author
ORCID:
0000-0001-8054-8751


Publisher:
Royal Society of Chemistry
Journal:
Dalton Transactions More from this journal
Volume:
48
Pages:
16099-16107
Publication date:
2019-10-09
Acceptance date:
2019-10-08
DOI:
EISSN:
1477-9234
ISSN:
1477-9226
Pmid:
31617518


Language:
English
Keywords:
Pubs id:
pubs:1063662
UUID:
uuid:aeedd5af-be48-4b3c-890b-b440684d75e5
Local pid:
pubs:1063662
Source identifiers:
1063662
Deposit date:
2019-10-24

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