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

doi:10.1021/acs.inorgchem.7b02964

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

Chemistry (Twin Cities)

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

34 Scopus citations

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 language	English (US)
Pages (from-to)	2064-2071
Number of pages	8
Journal	Inorganic chemistry
Volume	57
Issue number	4
DOIs	https://doi.org/10.1021/acs.inorgchem.7b02964
State	Published - Feb 19 2018

Bibliographical note

Funding Information:
C.J.C. acknowledges the U.S. National Science Foundation (CHE-1361595) and J.A.B. the US Army Research Office (66672-CH W911NF-15-1-0454) for financial support and the Minnesota Supercomputing Institute (MSI) at the University of Minnesota for providing resources that contributed to the research results reported within this paper.

Publisher Copyright:
© 2018 American Chemical Society.

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10.1021/acs.inorgchem.7b02964

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

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.",

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note = "Funding Information: C.J.C. acknowledges the U.S. National Science Foundation (CHE-1361595) and J.A.B. the US Army Research Office (66672-CH W911NF-15-1-0454) for financial support and the Minnesota Supercomputing Institute (MSI) at the University of Minnesota for providing resources that contributed to the research results reported within this paper. Publisher Copyright: {\textcopyright} 2018 American Chemical Society.",

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doi = "10.1021/acs.inorgchem.7b02964",

language = "English (US)",

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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

N1 - Funding Information: C.J.C. acknowledges the U.S. National Science Foundation (CHE-1361595) and J.A.B. the US Army Research Office (66672-CH W911NF-15-1-0454) for financial support and the Minnesota Supercomputing Institute (MSI) at the University of Minnesota for providing resources that contributed to the research results reported within this paper. Publisher Copyright: © 2018 American Chemical Society.

PY - 2018/2/19

Y1 - 2018/2/19

N2 - 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.

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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AN - SCOPUS:85042218463

SN - 0020-1669

VL - 57

SP - 2064

EP - 2071

JO - Inorganic chemistry

JF - Inorganic chemistry

IS - 4

ER -

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

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