Dizinc Lactide Polymerization Catalysts: Hyperactivity by Control of Ligand Conformation and Metallic Cooperativity.

ABSTRACT: 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) ).

SUBMITTER: Thevenon A 

PROVIDER: S-EPMC5089563 | biostudies-literature | 2016 Jul

REPOSITORIES: biostudies-literature