Structural and mechanistic studies of bis(phenolato)amine zinc(II) catalysts for the polymerization of ε-caprolactone

Carter M. Silvernail, Letitia J. Yao, Lyndal M R Hill, Marc A. Hillmyer, William B. Tolman

Research output: Contribution to journalArticlepeer-review

104 Scopus citations

Abstract

The syntheses, characterization, ecaprolactone (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-ε-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.

Original languageEnglish (US)
Pages (from-to)6565-6574
Number of pages10
JournalInorganic Chemistry
Volume46
Issue number16
DOIs
StatePublished - Aug 6 2007

Fingerprint Dive into the research topics of 'Structural and mechanistic studies of bis(phenolato)amine zinc(II) catalysts for the polymerization of ε-caprolactone'. Together they form a unique fingerprint.

Cite this