Structural and mechanistic studies of bis(phenolato)amine zinc(II) catalysts for the polymerization of epsilon-caprolactone.
The syntheses, characterization, epsilon-caprolactone (CL) polymerization activity, and kinetics investigation of two zinc(II) bis(phenolato)amine complexes L2Zn2 are reported (L = methylamino-N,N-bis(2-methylene-4,6-di-tert-butylphenolato) and/or methylamino-N,N-bis(2-methylene-4-adamantyl-6-tert-butylphenolato)). X-ray crystallographic and 1H NMR studies, including NOESY and PGSE experiments, provided insight into the solid and solution state structures, respectively, as well as evidence for the catalytically active species responsible for the ring-opening polymerization of CL. Additionally, solution polymerizations and kinetic experiments involving (L1)2Zn2 in the presence of benzyl alcohol (BnOH) were performed to elucidate the influence of catalyst structure, solvent, and the concentration dependence of the catalytically active species, CL, and BnOH on the rate and control of poly-epsilon-caprolactone (PCL) formation. The structural, polymerization, and kinetic data support equilibria involving both mononuclear and dinuclear forms of (L1)2Zn2 as well as a monomer-activated route to PCL.
Silvernail
Carter M
CM
Department of Chemistry, University of Minnesota, Minneapolis, MN 55455, USA.
Yao
Letitia J
LJ
Hill
Lyndal M R
LM
Hillmyer
Marc A
MA
Tolman
William B
WB
D002208:Caproates / Q000737:chemistry*; D002384:Catalysis; D002621:Chemistry / Q000379:methods*; D018360:Crystallography, X-Ray / Q000379:methods; D007700:Kinetics; D007783:Lactones / Q000737:chemistry*; D008024:Ligands; D009682:Magnetic Resonance Spectroscopy; D008670:Metals / Q000737:chemistry; D008956:Models, Chemical; D008958:Models, Molecular; D011108:Polymers / Q000737:chemistry; D015032:Zinc / Q000737:chemistry*; D017967:Zinc Compounds / Q000737:chemistry
D002208:Caproates; D007783:Lactones; D008024:Ligands; D008670:Metals; D011108:Polymers; D017967:Zinc Compounds; C121056:caprolactone; D015032:Zinc