TY - JOUR
T1 - Structural and mechanistic studies of bis(phenolato)amine zinc(II) catalysts for the polymerization of ε-caprolactone
AU - Silvernail, Carter M.
AU - Yao, Letitia J.
AU - Hill, Lyndal M R
AU - Hillmyer, Marc A.
AU - Tolman, William B.
PY - 2007/8/6
Y1 - 2007/8/6
N2 - 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.
AB - 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.
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U2 - 10.1021/ic700581s
DO - 10.1021/ic700581s
M3 - Article
C2 - 17630684
AN - SCOPUS:34548036719
SN - 0020-1669
VL - 46
SP - 6565
EP - 6574
JO - Inorganic chemistry
JF - Inorganic chemistry
IS - 16
ER -