The Role of Alkoxide Initiator, Spin State, and Oxidation State in Ring-Opening Polymerization of ϵ-Caprolactone Catalyzed by Iron Bis(imino)pyridine Complexes

Manuel A. Ortuño, Büsra Dereli, Kayla R.Delle Chiaie, Ashley B. Biernesser, Miao Qi, Jeffery A. Byers, Chris Cramer

Research output: Contribution to journalArticle

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Abstract

Density functional theory (DFT) is employed to characterize in detail the mechanism for the ring-opening polymerization (ROP) of ϵ-caprolactone catalyzed by iron alkoxide complexes bearing redox-active bis(imino)pyridine ligands. The combination of iron with the non-innocent bis(imino)pyridine ligand permits comparison of catalytic activity as a function of oxidation state (and overall spin state). The reactivities of aryl oxide versus alkoxide initiators for the ROP of ϵ-caprolactone are also examined. An experimental test of a computational prediction reveals an Fe(III) bis(imino)pyridine bis-neopentoxide complex to be competent for ROP of ϵ-caprolactone.

Original languageEnglish (US)
Pages (from-to)2064-2071
Number of pages8
JournalInorganic Chemistry
Volume57
Issue number4
DOIs
StatePublished - Feb 19 2018

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Ring opening polymerization
alkoxides
initiators
pyridines
Iron
polymerization
iron
Oxidation
oxidation
rings
Bearings (structural)
Ligands
ligands
Oxides
Density functional theory
catalytic activity
Catalyst activity
reactivity
density functional theory
oxides

PubMed: MeSH publication types

  • Journal Article

Cite this

The Role of Alkoxide Initiator, Spin State, and Oxidation State in Ring-Opening Polymerization of ϵ-Caprolactone Catalyzed by Iron Bis(imino)pyridine Complexes. / Ortuño, Manuel A.; Dereli, Büsra; Chiaie, Kayla R.Delle; Biernesser, Ashley B.; Qi, Miao; Byers, Jeffery A.; Cramer, Chris.

In: Inorganic Chemistry, Vol. 57, No. 4, 19.02.2018, p. 2064-2071.

Research output: Contribution to journalArticle

Ortuño, Manuel A. ; Dereli, Büsra ; Chiaie, Kayla R.Delle ; Biernesser, Ashley B. ; Qi, Miao ; Byers, Jeffery A. ; Cramer, Chris. / The Role of Alkoxide Initiator, Spin State, and Oxidation State in Ring-Opening Polymerization of ϵ-Caprolactone Catalyzed by Iron Bis(imino)pyridine Complexes. In: Inorganic Chemistry. 2018 ; Vol. 57, No. 4. pp. 2064-2071.
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AU - Ortuño, Manuel A.

AU - Dereli, Büsra

AU - Chiaie, Kayla R.Delle

AU - Biernesser, Ashley B.

AU - Qi, Miao

AU - Byers, Jeffery A.

AU - Cramer, Chris

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AB - Density functional theory (DFT) is employed to characterize in detail the mechanism for the ring-opening polymerization (ROP) of ϵ-caprolactone catalyzed by iron alkoxide complexes bearing redox-active bis(imino)pyridine ligands. The combination of iron with the non-innocent bis(imino)pyridine ligand permits comparison of catalytic activity as a function of oxidation state (and overall spin state). The reactivities of aryl oxide versus alkoxide initiators for the ROP of ϵ-caprolactone are also examined. An experimental test of a computational prediction reveals an Fe(III) bis(imino)pyridine bis-neopentoxide complex to be competent for ROP of ϵ-caprolactone.

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