Dizinc Lactide Polymerization Catalysts: Hyperactivity by Control of Ligand Conformation and Metallic Cooperativity.
Understanding how to moderate and improve catalytic activity is critical to improving degradable polymer production. Here, di- and monozinc catalysts, coordinated by bis(imino)diphenylamido ligands, show remarkable activities and allow determination of the factors controlling performance. In most cases, the dizinc catalysts significantly out-perform the monozinc analogs. Further, for the best dizinc catalyst, the ligand conformation controls activity: the catalyst with "folded" ligand conformation shows turnover frequency (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) ). Dizinc 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) ).
Department of Chemistry, Imperial College London, South Kensington, UK.
Arnaud
0000-0002-5543-6595
A
Thevenon
Department of Chemistry, Imperial College London, South Kensington, UK.
Charles
0000-0002-1851-8612
C
Romain
Department of Chemistry, University of Otago, Dunedin, New Zealand.
Michael S
0000-0002-3327-3975
MS
Bennington
Department of Chemistry, Imperial College London, South Kensington, UK.
Andrew J P
AJ
White
Department of Chemistry, University of Otago, Dunedin, New Zealand.
Hannah J
0000-0003-1193-7352
HJ
Davidson
Department of Chemistry, University of Otago, Dunedin, New Zealand. sbrooker@chemistry.otago.ac.nz.
Sally
0000-0002-5878-8238
S
Brooker
Department of Chemistry, Imperial College London, South Kensington, UK. c.k.williams@imperial.ac.uk.
Charlotte K
0000-0002-0734-1575
CK
Williams
dinuclear zinc complexes; homogeneous catalysis; metal-metal cooperativity; ring-opening polymerization; structure-activity relationship