Di-zinc Lactide Polymerization Catalysts: Hyper-Activity by Control of Ligand Conformation and Metallic Cooperativity
File(s)
Accepted version
Author(s)
Type
Journal Article
Abstract
Understanding how to moderate and improve catalytic activity is critical to improving degradable polymer production. Here, di- and mono-zinc catalysts, coordinated by bis(imino)diphenylamido ligands, show remarkable activities and allow determination of the factors controlling performance. In most cases, the di-zinc catalysts significantly out-perform the mono-zinc analogues. Further, for the best di-zinc catalyst, the ligand conformation controls activity: the catalyst with ‘folded’ ligand conformations show TOF values up to 60,000 h-1 (0.1 mol% loading, 298 K, [LA] = 1 M), whilst that with a ‘planar’ conformation is much slower, under similar conditions (TOF = 30 h-1). Di-zinc catalysts also perform very well under immortal conditions, showing improved control, and are able to tolerate loadings as low as 0.002 mol% whilst conserving high activity (TOF = 12,500 h-1).
Date Issued
2016-06-13
Date Acceptance
2016-04-12
Citation
Angewandte Chemie - International Edition, 2016, 55 (30), pp.8680-8685
ISSN
1433-7851
Publisher
Wiley
Start Page
8680
End Page
8685
Journal / Book Title
Angewandte Chemie - International Edition
Volume
55
Issue
30
Copyright Statement
© 2016 The Authors. Published by Wiley-VCH Verlag GmbH & Co.KGaA. This is an open access article under the terms of the CreativeCommons Attribution Non-Commercial License, which permits use,distribution and reproduction in any medium, provided the originalwork is properly cited, and is not used for commercial purposes.
License URL
Sponsor
Engineering & Physical Science Research Council (EPSRC)
Engineering & Physical Science Research Council (E
Engineering & Physical Science Research Council (EPSRC)
Engineering & Physical Science Research Council (E
Grant Number
EP/K035274/1
EP/K014668/1
EP/K014676/1
EP/L017393/1
Subjects
dinuclear zinc complexes
homogeneous catalysis
metal-metal cooperativity
ring-opening polymerization
structure-activity relationship
Organic Chemistry
03 Chemical Sciences
Publication Status
Published