Copolymerisation of Propylene Oxide and Carbon Dioxide by Dinuclear Cobalt Porphyrins

Handle URI:
http://hdl.handle.net/10754/597880
Title:
Copolymerisation of Propylene Oxide and Carbon Dioxide by Dinuclear Cobalt Porphyrins
Authors:
Anderson, Carly E.; Vagin, Sergei I.; Hammann, Markus; Zimmermann, Leander; Rieger, Bernhard
Abstract:
Two dinuclear cobalt porphyrins comprising different structural tethering motifs at the porphyrin periphery were synthesised, along with a representative mononuclear cobalt porphyrin, and their catalytic activities tested towards carbon dioxide-propylene oxide copolymerisation in the presence of bis(triphenylphosphoranyl)ammonium chloride cocatalyst. The catalytic activities of the mononuclear and the bis-para-tethered dinuclear cobalt porphyrin with selective formation of poly(propylene carbonate) are largely comparable, showing no benefit of dinuclearity in contrast to the case of cobalt salen complexes and suggesting that polymer growth proceeds exclusively from one metal centre. The alternative bis-ortho-tethered porphyrin demonstrated considerably reduced activity, with dominant formation of cyclic propylene carbonate, as a result of hindered substrate approach at the metal centre. Time-resolved UV/Vis spectroscopic studies suggested a general intolerance of the cobalt(III) porphyrin catalysts towards the copolymerisation conditions in the absence of carbon dioxide pressure, leading to catalytically inactive cobalt(II) species. In the presence of carbon dioxide, the bis-ortho-tethered catalyst showed the fastest deactivation, which is related to an unfavourable steric arrangement of the linker fragment, as was also confirmed by NMR spectroscopic measurements. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Citation:
Anderson CE, Vagin SI, Hammann M, Zimmermann L, Rieger B (2013) Copolymerisation of Propylene Oxide and Carbon Dioxide by Dinuclear Cobalt Porphyrins. ChemCatChem 5: 3269–3280. Available: http://dx.doi.org/10.1002/cctc.201300307.
Publisher:
Wiley-Blackwell
Journal:
ChemCatChem
KAUST Grant Number:
UK-C0020; KSA-C0069
Issue Date:
18-Sep-2013
DOI:
10.1002/cctc.201300307
Type:
Article
ISSN:
1867-3880
Sponsors:
CEA gratefully acknowledges the King Abdullah University of Science and Technology (KAUST), Award No. UK-C0020, KSA-C0069, for financial support.
Appears in Collections:
Publications Acknowledging KAUST Support

Full metadata record

DC FieldValue Language
dc.contributor.authorAnderson, Carly E.en
dc.contributor.authorVagin, Sergei I.en
dc.contributor.authorHammann, Markusen
dc.contributor.authorZimmermann, Leanderen
dc.contributor.authorRieger, Bernharden
dc.date.accessioned2016-02-25T12:58:15Zen
dc.date.available2016-02-25T12:58:15Zen
dc.date.issued2013-09-18en
dc.identifier.citationAnderson CE, Vagin SI, Hammann M, Zimmermann L, Rieger B (2013) Copolymerisation of Propylene Oxide and Carbon Dioxide by Dinuclear Cobalt Porphyrins. ChemCatChem 5: 3269–3280. Available: http://dx.doi.org/10.1002/cctc.201300307.en
dc.identifier.issn1867-3880en
dc.identifier.doi10.1002/cctc.201300307en
dc.identifier.urihttp://hdl.handle.net/10754/597880en
dc.description.abstractTwo dinuclear cobalt porphyrins comprising different structural tethering motifs at the porphyrin periphery were synthesised, along with a representative mononuclear cobalt porphyrin, and their catalytic activities tested towards carbon dioxide-propylene oxide copolymerisation in the presence of bis(triphenylphosphoranyl)ammonium chloride cocatalyst. The catalytic activities of the mononuclear and the bis-para-tethered dinuclear cobalt porphyrin with selective formation of poly(propylene carbonate) are largely comparable, showing no benefit of dinuclearity in contrast to the case of cobalt salen complexes and suggesting that polymer growth proceeds exclusively from one metal centre. The alternative bis-ortho-tethered porphyrin demonstrated considerably reduced activity, with dominant formation of cyclic propylene carbonate, as a result of hindered substrate approach at the metal centre. Time-resolved UV/Vis spectroscopic studies suggested a general intolerance of the cobalt(III) porphyrin catalysts towards the copolymerisation conditions in the absence of carbon dioxide pressure, leading to catalytically inactive cobalt(II) species. In the presence of carbon dioxide, the bis-ortho-tethered catalyst showed the fastest deactivation, which is related to an unfavourable steric arrangement of the linker fragment, as was also confirmed by NMR spectroscopic measurements. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.en
dc.description.sponsorshipCEA gratefully acknowledges the King Abdullah University of Science and Technology (KAUST), Award No. UK-C0020, KSA-C0069, for financial support.en
dc.publisherWiley-Blackwellen
dc.subjectCarbon dioxidecobalten
dc.subjectCopolymerisationen
dc.subjectEpoxidesen
dc.subjectPorphyrinoidsen
dc.titleCopolymerisation of Propylene Oxide and Carbon Dioxide by Dinuclear Cobalt Porphyrinsen
dc.typeArticleen
dc.identifier.journalChemCatChemen
dc.contributor.institutionTechnische Universitat Munchen, Munich, Germanyen
kaust.grant.numberUK-C0020en
kaust.grant.numberKSA-C0069en
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