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Cooperative Hydrogen-Bond Pairing in Organocatalytic Ring-Opening Polymerization.

Kazakov OI, Datta PP, Isajani M, Kiesewetter ET, Kiesewetter MK - Macromolecules (2014)

Bottom Line: In this work, several of the most active cocatalyst pairs are shown by (1)H NMR binding studies to be highly associated in solution, dominating all other known noncovalent catalyst/reagent interactions during ROP.One strongly binding catalyst pair behaves kinetically as a unimolecular catalyst species.The high selectivity and activity exhibited by these ROP organocatalysts are attributed to the strong binding between the two cocatalysts, and the predictive utility of these binding parameters is applied for the discovery of a new, highly active cocatalyst pair.

View Article: PubMed Central - PubMed

Affiliation: Department of Chemistry, University of Rhode Island , Kingston, Rhode Island 02881, United States.

ABSTRACT
Thiourea (TU)/amine base cocatalysts are commonly employed for well-controlled, highly active "living" organocatalytic ring-opening polymerizations (ROPs) of cyclic esters and carbonates. In this work, several of the most active cocatalyst pairs are shown by (1)H NMR binding studies to be highly associated in solution, dominating all other known noncovalent catalyst/reagent interactions during ROP. One strongly binding catalyst pair behaves kinetically as a unimolecular catalyst species. The high selectivity and activity exhibited by these ROP organocatalysts are attributed to the strong binding between the two cocatalysts, and the predictive utility of these binding parameters is applied for the discovery of a new, highly active cocatalyst pair.

No MeSH data available.


H-Bonding Mechanismfor the ROP of δ-Valerolactone
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Cooperative Hydrogen-Bond Pairing in Organocatalytic Ring-Opening Polymerization.

Kazakov OI, Datta PP, Isajani M, Kiesewetter ET, Kiesewetter MK - Macromolecules (2014)

H-Bonding Mechanismfor the ROP of δ-Valerolactone
© Copyright Policy
Related In: Results  -  Collection

License
Show All Figures
getmorefigures.php?uid=PMC4230384&req=5

sch1: H-Bonding Mechanismfor the ROP of δ-Valerolactone
Bottom Line: In this work, several of the most active cocatalyst pairs are shown by (1)H NMR binding studies to be highly associated in solution, dominating all other known noncovalent catalyst/reagent interactions during ROP.One strongly binding catalyst pair behaves kinetically as a unimolecular catalyst species.The high selectivity and activity exhibited by these ROP organocatalysts are attributed to the strong binding between the two cocatalysts, and the predictive utility of these binding parameters is applied for the discovery of a new, highly active cocatalyst pair.

View Article: PubMed Central - PubMed

Affiliation: Department of Chemistry, University of Rhode Island , Kingston, Rhode Island 02881, United States.

ABSTRACT
Thiourea (TU)/amine base cocatalysts are commonly employed for well-controlled, highly active "living" organocatalytic ring-opening polymerizations (ROPs) of cyclic esters and carbonates. In this work, several of the most active cocatalyst pairs are shown by (1)H NMR binding studies to be highly associated in solution, dominating all other known noncovalent catalyst/reagent interactions during ROP. One strongly binding catalyst pair behaves kinetically as a unimolecular catalyst species. The high selectivity and activity exhibited by these ROP organocatalysts are attributed to the strong binding between the two cocatalysts, and the predictive utility of these binding parameters is applied for the discovery of a new, highly active cocatalyst pair.

No MeSH data available.