Nickel-Catalyzed Coupling of Carbon Dioxide with Cyclohexene Oxide by Well-Characterized Bis(N-Heterocyclic Carbene) Carbazolide Complexes

Ting Yu Lee, Yi Jen Lin, Yuan Zhen Chang, Li Shin Huang, Bao Tsan Ko, Jui Hsien Huang

Research output: Contribution to journalArticle

7 Citations (Scopus)

Abstract

The facile synthesis, structural characterization, and catalytic studies for CO2/epoxide coupling of nickel acetates based on carbazolide-bis(NHC) (NHC = N-heterocyclic carbene) were reported. Treatment of 3,6-di-tert-butyl-1,8-bis(3-alkylimidazolium-1-yl)carbazole salt proligands (bis(R-Im-X)Cz, R = benzyl (Bn), n-butyl (nBu), methyl (Me), X = Br or I) with nickel acetate tetrahydrate in the presence of excess triethylamine generated monomeric four-coordinate nickel complexes [(bis(R-Im)Cz)Ni(OAc)] (R = Bn (3), R = nBu (4), and R = Me (5)). Single-crystal X-ray diffraction of Ni complexes 4 and 5 indicates that the bis(NHC)-carbazolide fragment behaves as a CNC-tridentate pincer ligand to coordinate the metal center, and the ancillary acetate group assumes a terminal acetate bonding mode. Catalysis for coupling of carbon dioxide with cyclohexene oxide (CHO) by these carbazolide-bis(NHC)-ligated Ni complexes was systematically examined. Experimental results displayed that cycloaddition of CHO and CO2 catalyzed with complex 4 could give cyclohexene carbonate (CHC) with >99% cis-isomer selectivity on using low catalyst concentrations and high reaction temperature, whereas catalyst 3 was able to copolymerize CHO and CO2 to afford a narrowly dispersed and perfectly alternating poly(cyclohexene carbonate) (PCHC) as the major product at the higher catalyst loadings and lower copolymerization temperature. This is the first time that the air-stable bis(NHC)-carbazolide nickel(II) acetate is an effective and versatile catalyst for the formation of either biodegradable PCHCs or cis-CHCs.

Original languageEnglish
Pages (from-to)291-297
Number of pages7
JournalOrganometallics
Volume36
Issue number2
DOIs
Publication statusPublished - 2017 Jan 23

Fingerprint

carbenes
Nickel
Carbon Dioxide
carbon dioxide
acetates
nickel
Catalysts
oxides
catalysts
Acetates
carbonates
Cycloaddition
Catalyst selectivity
Carbonates
Epoxy Compounds
Isomers
Copolymerization
epoxy compounds
Catalysis
carbazoles

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

Cite this

Lee, Ting Yu ; Lin, Yi Jen ; Chang, Yuan Zhen ; Huang, Li Shin ; Ko, Bao Tsan ; Huang, Jui Hsien. / Nickel-Catalyzed Coupling of Carbon Dioxide with Cyclohexene Oxide by Well-Characterized Bis(N-Heterocyclic Carbene) Carbazolide Complexes. In: Organometallics. 2017 ; Vol. 36, No. 2. pp. 291-297.
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title = "Nickel-Catalyzed Coupling of Carbon Dioxide with Cyclohexene Oxide by Well-Characterized Bis(N-Heterocyclic Carbene) Carbazolide Complexes",
abstract = "The facile synthesis, structural characterization, and catalytic studies for CO2/epoxide coupling of nickel acetates based on carbazolide-bis(NHC) (NHC = N-heterocyclic carbene) were reported. Treatment of 3,6-di-tert-butyl-1,8-bis(3-alkylimidazolium-1-yl)carbazole salt proligands (bis(R-Im-X)Cz, R = benzyl (Bn), n-butyl (nBu), methyl (Me), X = Br or I) with nickel acetate tetrahydrate in the presence of excess triethylamine generated monomeric four-coordinate nickel complexes [(bis(R-Im)Cz)Ni(OAc)] (R = Bn (3), R = nBu (4), and R = Me (5)). Single-crystal X-ray diffraction of Ni complexes 4 and 5 indicates that the bis(NHC)-carbazolide fragment behaves as a CNC-tridentate pincer ligand to coordinate the metal center, and the ancillary acetate group assumes a terminal acetate bonding mode. Catalysis for coupling of carbon dioxide with cyclohexene oxide (CHO) by these carbazolide-bis(NHC)-ligated Ni complexes was systematically examined. Experimental results displayed that cycloaddition of CHO and CO2 catalyzed with complex 4 could give cyclohexene carbonate (CHC) with >99{\%} cis-isomer selectivity on using low catalyst concentrations and high reaction temperature, whereas catalyst 3 was able to copolymerize CHO and CO2 to afford a narrowly dispersed and perfectly alternating poly(cyclohexene carbonate) (PCHC) as the major product at the higher catalyst loadings and lower copolymerization temperature. This is the first time that the air-stable bis(NHC)-carbazolide nickel(II) acetate is an effective and versatile catalyst for the formation of either biodegradable PCHCs or cis-CHCs.",
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Nickel-Catalyzed Coupling of Carbon Dioxide with Cyclohexene Oxide by Well-Characterized Bis(N-Heterocyclic Carbene) Carbazolide Complexes. / Lee, Ting Yu; Lin, Yi Jen; Chang, Yuan Zhen; Huang, Li Shin; Ko, Bao Tsan; Huang, Jui Hsien.

In: Organometallics, Vol. 36, No. 2, 23.01.2017, p. 291-297.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Nickel-Catalyzed Coupling of Carbon Dioxide with Cyclohexene Oxide by Well-Characterized Bis(N-Heterocyclic Carbene) Carbazolide Complexes

AU - Lee, Ting Yu

AU - Lin, Yi Jen

AU - Chang, Yuan Zhen

AU - Huang, Li Shin

AU - Ko, Bao Tsan

AU - Huang, Jui Hsien

PY - 2017/1/23

Y1 - 2017/1/23

N2 - The facile synthesis, structural characterization, and catalytic studies for CO2/epoxide coupling of nickel acetates based on carbazolide-bis(NHC) (NHC = N-heterocyclic carbene) were reported. Treatment of 3,6-di-tert-butyl-1,8-bis(3-alkylimidazolium-1-yl)carbazole salt proligands (bis(R-Im-X)Cz, R = benzyl (Bn), n-butyl (nBu), methyl (Me), X = Br or I) with nickel acetate tetrahydrate in the presence of excess triethylamine generated monomeric four-coordinate nickel complexes [(bis(R-Im)Cz)Ni(OAc)] (R = Bn (3), R = nBu (4), and R = Me (5)). Single-crystal X-ray diffraction of Ni complexes 4 and 5 indicates that the bis(NHC)-carbazolide fragment behaves as a CNC-tridentate pincer ligand to coordinate the metal center, and the ancillary acetate group assumes a terminal acetate bonding mode. Catalysis for coupling of carbon dioxide with cyclohexene oxide (CHO) by these carbazolide-bis(NHC)-ligated Ni complexes was systematically examined. Experimental results displayed that cycloaddition of CHO and CO2 catalyzed with complex 4 could give cyclohexene carbonate (CHC) with >99% cis-isomer selectivity on using low catalyst concentrations and high reaction temperature, whereas catalyst 3 was able to copolymerize CHO and CO2 to afford a narrowly dispersed and perfectly alternating poly(cyclohexene carbonate) (PCHC) as the major product at the higher catalyst loadings and lower copolymerization temperature. This is the first time that the air-stable bis(NHC)-carbazolide nickel(II) acetate is an effective and versatile catalyst for the formation of either biodegradable PCHCs or cis-CHCs.

AB - The facile synthesis, structural characterization, and catalytic studies for CO2/epoxide coupling of nickel acetates based on carbazolide-bis(NHC) (NHC = N-heterocyclic carbene) were reported. Treatment of 3,6-di-tert-butyl-1,8-bis(3-alkylimidazolium-1-yl)carbazole salt proligands (bis(R-Im-X)Cz, R = benzyl (Bn), n-butyl (nBu), methyl (Me), X = Br or I) with nickel acetate tetrahydrate in the presence of excess triethylamine generated monomeric four-coordinate nickel complexes [(bis(R-Im)Cz)Ni(OAc)] (R = Bn (3), R = nBu (4), and R = Me (5)). Single-crystal X-ray diffraction of Ni complexes 4 and 5 indicates that the bis(NHC)-carbazolide fragment behaves as a CNC-tridentate pincer ligand to coordinate the metal center, and the ancillary acetate group assumes a terminal acetate bonding mode. Catalysis for coupling of carbon dioxide with cyclohexene oxide (CHO) by these carbazolide-bis(NHC)-ligated Ni complexes was systematically examined. Experimental results displayed that cycloaddition of CHO and CO2 catalyzed with complex 4 could give cyclohexene carbonate (CHC) with >99% cis-isomer selectivity on using low catalyst concentrations and high reaction temperature, whereas catalyst 3 was able to copolymerize CHO and CO2 to afford a narrowly dispersed and perfectly alternating poly(cyclohexene carbonate) (PCHC) as the major product at the higher catalyst loadings and lower copolymerization temperature. This is the first time that the air-stable bis(NHC)-carbazolide nickel(II) acetate is an effective and versatile catalyst for the formation of either biodegradable PCHCs or cis-CHCs.

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