skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Catalytic activity of a series of Zn(II) phenoxides for the copolymerization of epoxides and carbon dioxide

Abstract

A series of zinc phenoxides of the general formula (2,6-R{sub 2}C{sub 6}H{sub 3}O){sub 2}Zn(base){sub 2} [R = Ph, {sup t}Bu, {sup i}Pr, base = Et{sub 2}O, THF, or propylene carbonate] and (2,4,6-Me{sub 3}C{sub 6}H{sub 2}O){sub 2}Zn(pyridine){sub 2} have been synthesized and characterized in the solid state by X-ray crystallography. All complexes crystallized as four-coordinate monomers with highly distorted tetrahedral geometry about the zinc center. The angles between the two sterically encumbering phenoxide ligands were found to be significantly more obtuse than the corresponding angles between the two smaller neutral base ligands, having average values of 140{degree} and 95{degree}, respectively. In a noninteracting solvent such as benzene or methylene chloride at ambient temperature, the ancillary base ligands are extensively dissociated from the zinc center, with the degree of dissociation being dependent on the base as well as the substituents on the phenolate ligands. That is, stronger ligand binding was found in zinc centers containing electron-donating tert-butyl substituents as opposed to electron-withdrawing phenyl substituents. In all instances, the order of ligand binding was pyridine > THF > epoxides. These bis(phenoxide) derivatives of zinc were shown to be very effective catalysts for the copolymerization of cyclohexene oxide and CO{sub 2} in the absencemore » of strongly coordinating solvents, to afford high-molecular-weight polycarbonate (M{sub w} ranging from 45 x 10{sup 3} to 173 x 10{sup 3} Da) with low levels of polyether linkages. However, under similar conditions, these zinc complexes only coupled propylene oxide and CO{sub 2} to produce cyclic propylene carbonate. Nevertheless, these bis(phenoxide) derivatives of zinc were competent at terpolymerization of cyclohexene oxide/propylene oxide/CO{sub 2} with little cyclic propylene carbonate formation at low propylene oxide loadings. While CO{sub 2} showed no reactivity with the sterically encumbered zinc bis(phenoxides), e.g., (2,6-di-tert-butylphenoxide){sub 2}Zn(pyridine){sub 2} to provide the corresponding aryl carbonate zinc derivative. At the same time, both sterically hindered and sterically nonhindered phenoxide derivatives of zinc served to ring-open epoxide, i.e., were effective catalysts for the homopolymerization of epoxide to polyethers. The relevance of these reactivity patterns to the initiation step of the copolymerization process involving these monomeric zinc complexes is discussed.« less

Authors:
; ; ; ; ; ; ; ;
Publication Date:
Research Org.:
Texas A and M Univ., College Station, TX (US)
OSTI Identifier:
20014095
Resource Type:
Journal Article
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 121; Journal Issue: 1; Other Information: PBD: 13 Jan 1999; Journal ID: ISSN 0002-7863
Country of Publication:
United States
Language:
English
Subject:
32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATION; CATALYSTS; ZINC COMPOUNDS; PHENOXY RADICALS; ALKYL RADICALS; EPOXIDES; CARBON DIOXIDE; COPOLYMERIZATION

Citation Formats

Darensbourg, D J, Holtcamp, M W, Struck, G E, Zimmer, M S, Niezgoda, S A, Rainey, P, Robertson, J B, Draper, J D, and Reibenspies, J H. Catalytic activity of a series of Zn(II) phenoxides for the copolymerization of epoxides and carbon dioxide. United States: N. p., 1999. Web. doi:10.1021/ja9826284.
Darensbourg, D J, Holtcamp, M W, Struck, G E, Zimmer, M S, Niezgoda, S A, Rainey, P, Robertson, J B, Draper, J D, & Reibenspies, J H. Catalytic activity of a series of Zn(II) phenoxides for the copolymerization of epoxides and carbon dioxide. United States. doi:10.1021/ja9826284.
Darensbourg, D J, Holtcamp, M W, Struck, G E, Zimmer, M S, Niezgoda, S A, Rainey, P, Robertson, J B, Draper, J D, and Reibenspies, J H. Wed . "Catalytic activity of a series of Zn(II) phenoxides for the copolymerization of epoxides and carbon dioxide". United States. doi:10.1021/ja9826284.
@article{osti_20014095,
title = {Catalytic activity of a series of Zn(II) phenoxides for the copolymerization of epoxides and carbon dioxide},
author = {Darensbourg, D J and Holtcamp, M W and Struck, G E and Zimmer, M S and Niezgoda, S A and Rainey, P and Robertson, J B and Draper, J D and Reibenspies, J H},
abstractNote = {A series of zinc phenoxides of the general formula (2,6-R{sub 2}C{sub 6}H{sub 3}O){sub 2}Zn(base){sub 2} [R = Ph, {sup t}Bu, {sup i}Pr, base = Et{sub 2}O, THF, or propylene carbonate] and (2,4,6-Me{sub 3}C{sub 6}H{sub 2}O){sub 2}Zn(pyridine){sub 2} have been synthesized and characterized in the solid state by X-ray crystallography. All complexes crystallized as four-coordinate monomers with highly distorted tetrahedral geometry about the zinc center. The angles between the two sterically encumbering phenoxide ligands were found to be significantly more obtuse than the corresponding angles between the two smaller neutral base ligands, having average values of 140{degree} and 95{degree}, respectively. In a noninteracting solvent such as benzene or methylene chloride at ambient temperature, the ancillary base ligands are extensively dissociated from the zinc center, with the degree of dissociation being dependent on the base as well as the substituents on the phenolate ligands. That is, stronger ligand binding was found in zinc centers containing electron-donating tert-butyl substituents as opposed to electron-withdrawing phenyl substituents. In all instances, the order of ligand binding was pyridine > THF > epoxides. These bis(phenoxide) derivatives of zinc were shown to be very effective catalysts for the copolymerization of cyclohexene oxide and CO{sub 2} in the absence of strongly coordinating solvents, to afford high-molecular-weight polycarbonate (M{sub w} ranging from 45 x 10{sup 3} to 173 x 10{sup 3} Da) with low levels of polyether linkages. However, under similar conditions, these zinc complexes only coupled propylene oxide and CO{sub 2} to produce cyclic propylene carbonate. Nevertheless, these bis(phenoxide) derivatives of zinc were competent at terpolymerization of cyclohexene oxide/propylene oxide/CO{sub 2} with little cyclic propylene carbonate formation at low propylene oxide loadings. While CO{sub 2} showed no reactivity with the sterically encumbered zinc bis(phenoxides), e.g., (2,6-di-tert-butylphenoxide){sub 2}Zn(pyridine){sub 2} to provide the corresponding aryl carbonate zinc derivative. At the same time, both sterically hindered and sterically nonhindered phenoxide derivatives of zinc served to ring-open epoxide, i.e., were effective catalysts for the homopolymerization of epoxide to polyethers. The relevance of these reactivity patterns to the initiation step of the copolymerization process involving these monomeric zinc complexes is discussed.},
doi = {10.1021/ja9826284},
journal = {Journal of the American Chemical Society},
issn = {0002-7863},
number = 1,
volume = 121,
place = {United States},
year = {1999},
month = {1}
}