Zinc N-heterocyclic carbene complexes and their polymerization of d,l-lactide

Tryg R. Jensen; Chris P. Schaller; Marc A. Hillmyer; William B. Tolman

doi:10.1016/j.jorganchem.2005.07.070

Zinc N-heterocyclic carbene complexes and their polymerization of d,l-lactide

Tryg R. Jensen, Chris P. Schaller, Marc A. Hillmyer, William B. Tolman

Chemistry (Twin Cities)

Research output: Contribution to journal › Article › peer-review

128 Scopus citations

Abstract

A series of zinc complexes of monodentate N-heterocyclic carbenes (NHCs) and a new sterically bulky bidentate pyridyl-NHC ligand have been synthesized and characterized by spectroscopic and X-ray crystallographic methods. Dinuclear alkoxide complexes of monodentate NHC complexes with 2,4,6-trimethylphenyl substituents appear to form monomeric species in solution and show good control and activity for lactide polymerization, including mild stereoelectivity as indicated by formation of heterotactic-enriched polylactide in d,l-lactide polymerizations. Kinetics studies revealed an overall second order rate law, first order in [LA] and [catalyst]. Efforts to obtain Zn-alkoxide complexes of a more sterically hindered NHC with 2,6-diisopropylphenyl groups were unsuccessful due to Zn-NHC bond scission. Ligand dissociation was also observed in attempts to prepare Zn-alkoxide complexes of the bidentate pyridyl-NHC system, despite its chelating nature.

Original language	English (US)
Pages (from-to)	5881-5891
Number of pages	11
Journal	Journal of Organometallic Chemistry
Volume	690
Issue number	24-25
DOIs	https://doi.org/10.1016/j.jorganchem.2005.07.070
State	Published - Dec 1 2005

Bibliographical note

Funding Information:
Financial support from the NSF (CHE-023666) is gratefully acknowledged. C.P.S. wishes to acknowledge support from the NSF-RSEC program at the University of Minnesota. We thank Lyndal M.R. Hill, Benjamin E. Kucera, Victor G. Young, Jr., and the X-ray Crystallographic Laboratory at the University of Minnesota for the crystallographic determinations, and Dana Reed for assistance with mass spectrometry.

Keywords

Lactide
N-heterocyclic carbenes
Polylactide
Polymerization catalysis
Zinc

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abstract = "A series of zinc complexes of monodentate N-heterocyclic carbenes (NHCs) and a new sterically bulky bidentate pyridyl-NHC ligand have been synthesized and characterized by spectroscopic and X-ray crystallographic methods. Dinuclear alkoxide complexes of monodentate NHC complexes with 2,4,6-trimethylphenyl substituents appear to form monomeric species in solution and show good control and activity for lactide polymerization, including mild stereoelectivity as indicated by formation of heterotactic-enriched polylactide in d,l-lactide polymerizations. Kinetics studies revealed an overall second order rate law, first order in [LA] and [catalyst]. Efforts to obtain Zn-alkoxide complexes of a more sterically hindered NHC with 2,6-diisopropylphenyl groups were unsuccessful due to Zn-NHC bond scission. Ligand dissociation was also observed in attempts to prepare Zn-alkoxide complexes of the bidentate pyridyl-NHC system, despite its chelating nature.",

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note = "Funding Information: Financial support from the NSF (CHE-023666) is gratefully acknowledged. C.P.S. wishes to acknowledge support from the NSF-RSEC program at the University of Minnesota. We thank Lyndal M.R. Hill, Benjamin E. Kucera, Victor G. Young, Jr., and the X-ray Crystallographic Laboratory at the University of Minnesota for the crystallographic determinations, and Dana Reed for assistance with mass spectrometry. ",

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AB - A series of zinc complexes of monodentate N-heterocyclic carbenes (NHCs) and a new sterically bulky bidentate pyridyl-NHC ligand have been synthesized and characterized by spectroscopic and X-ray crystallographic methods. Dinuclear alkoxide complexes of monodentate NHC complexes with 2,4,6-trimethylphenyl substituents appear to form monomeric species in solution and show good control and activity for lactide polymerization, including mild stereoelectivity as indicated by formation of heterotactic-enriched polylactide in d,l-lactide polymerizations. Kinetics studies revealed an overall second order rate law, first order in [LA] and [catalyst]. Efforts to obtain Zn-alkoxide complexes of a more sterically hindered NHC with 2,6-diisopropylphenyl groups were unsuccessful due to Zn-NHC bond scission. Ligand dissociation was also observed in attempts to prepare Zn-alkoxide complexes of the bidentate pyridyl-NHC system, despite its chelating nature.

KW - Lactide

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KW - Polymerization catalysis

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Zinc N-heterocyclic carbene complexes and their polymerization of d,l-lactide

Abstract

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Keywords

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