Iron-catalysed ring-opening metathesis polymerization of olefins and mechanistic studies

Satoshi Takebayashi; Mark A. Iron; Moran Feller; Orestes Rivada-Wheelaghan; Gregory Leitus; Yael Diskin-Posner; Linda J.W. Shimon; Liat Avram; Raanan Carmieli; Sharon G. Wolf; Ilit Cohen-Ofri; Rajashekharayya A. Sanguramath; Roy Shenhar; Moris Eisen; David Milstein

doi:10.1038/s41929-022-00793-4

Iron-catalysed ring-opening metathesis polymerization of olefins and mechanistic studies

Satoshi Takebayashi^*, Mark A. Iron, Moran Feller, Orestes Rivada-Wheelaghan, Gregory Leitus, Yael Diskin-Posner, Linda J.W. Shimon, Liat Avram, Raanan Carmieli, Sharon G. Wolf, Ilit Cohen-Ofri, Rajashekharayya A. Sanguramath, Roy Shenhar, Moris Eisen, David Milstein^*

^*Corresponding author for this work

Institute of Chemistry

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

12 Scopus citations

Abstract

The olefin metathesis reaction is among the most widely applicable catalytic reactions for carbon–carbon double bond formation. Currently, Mo– and Ru–carbene catalysts are the most common choices for this reaction. It has been suggested that an iron-based catalyst would be a desirable economical and biocompatible substitute of the Ru catalysts; however, practical solutions in this regard are still lacking. Here, we report the discovery and mechanistic studies of three-coordinate iron(II) catalysts for ring-opening metathesis polymerization of olefins. Remarkably, their reactivity enabled the formation of polynorbornene with stereoregularity and high molecular weight (>10⁷ g mol^–1). The polymerization in the presence of styrene revealed cross metathesis reactivity with iron catalysts. Mechanistic studies suggest the possible role of metal–ligand cooperation in formation of the productive catalyst. This work opens the door to the development of iron complexes that can be economical and biocompatible catalysts for olefin metathesis reactions. [Figure not available: see fulltext.]

Original language	American English
Pages (from-to)	494-502
Number of pages	9
Journal	Nature Catalysis
Volume	5
Issue number	6
DOIs	https://doi.org/10.1038/s41929-022-00793-4
State	Published - Jun 2022

Bibliographical note

Funding Information:
This research was supported by the Israel Science Foundation (1721/13, D.M.) and the Japan Society for the Promotion of Science (18K14230, S.T.). Electron microscopy studies were supported in part by the Irving and Cherna Moskowitz Center for Nano and Bio-Nano Imaging at the Weizmann Institute of Science. This work was supported by Okinawa Institute of Science and Technology Graduate University instrumental analysis and engineering sections. S.T. thanks M. C. Roy for the assistance with solid-state NMR measurement. D.M. holds the Israel Matz Professorial Chair. All data are provided in the Supplementary Information. This manuscript is dedicated to the memory of Professor Robert H. Grubbs.

Publisher Copyright:
© 2022, The Author(s), under exclusive licence to Springer Nature Limited.

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Takebayashi, S., Iron, M. A., Feller, M., Rivada-Wheelaghan, O., Leitus, G., Diskin-Posner, Y., Shimon, L. J. W., Avram, L., Carmieli, R., Wolf, S. G., Cohen-Ofri, I., Sanguramath, R. A., Shenhar, R., Eisen, M., & Milstein, D. (2022). Iron-catalysed ring-opening metathesis polymerization of olefins and mechanistic studies. Nature Catalysis, 5(6), 494-502. https://doi.org/10.1038/s41929-022-00793-4

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title = "Iron-catalysed ring-opening metathesis polymerization of olefins and mechanistic studies",

abstract = "The olefin metathesis reaction is among the most widely applicable catalytic reactions for carbon–carbon double bond formation. Currently, Mo– and Ru–carbene catalysts are the most common choices for this reaction. It has been suggested that an iron-based catalyst would be a desirable economical and biocompatible substitute of the Ru catalysts; however, practical solutions in this regard are still lacking. Here, we report the discovery and mechanistic studies of three-coordinate iron(II) catalysts for ring-opening metathesis polymerization of olefins. Remarkably, their reactivity enabled the formation of polynorbornene with stereoregularity and high molecular weight (>107 g mol–1). The polymerization in the presence of styrene revealed cross metathesis reactivity with iron catalysts. Mechanistic studies suggest the possible role of metal–ligand cooperation in formation of the productive catalyst. This work opens the door to the development of iron complexes that can be economical and biocompatible catalysts for olefin metathesis reactions. [Figure not available: see fulltext.]",

author = "Satoshi Takebayashi and Iron, {Mark A.} and Moran Feller and Orestes Rivada-Wheelaghan and Gregory Leitus and Yael Diskin-Posner and Shimon, {Linda J.W.} and Liat Avram and Raanan Carmieli and Wolf, {Sharon G.} and Ilit Cohen-Ofri and Sanguramath, {Rajashekharayya A.} and Roy Shenhar and Moris Eisen and David Milstein",

note = "Funding Information: This research was supported by the Israel Science Foundation (1721/13, D.M.) and the Japan Society for the Promotion of Science (18K14230, S.T.). Electron microscopy studies were supported in part by the Irving and Cherna Moskowitz Center for Nano and Bio-Nano Imaging at the Weizmann Institute of Science. This work was supported by Okinawa Institute of Science and Technology Graduate University instrumental analysis and engineering sections. S.T. thanks M. C. Roy for the assistance with solid-state NMR measurement. D.M. holds the Israel Matz Professorial Chair. All data are provided in the Supplementary Information. This manuscript is dedicated to the memory of Professor Robert H. Grubbs. Publisher Copyright: {\textcopyright} 2022, The Author(s), under exclusive licence to Springer Nature Limited.",

year = "2022",

month = jun,

doi = "10.1038/s41929-022-00793-4",

language = "American English",

volume = "5",

pages = "494--502",

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Takebayashi, S, Iron, MA, Feller, M, Rivada-Wheelaghan, O, Leitus, G, Diskin-Posner, Y, Shimon, LJW, Avram, L, Carmieli, R, Wolf, SG, Cohen-Ofri, I, Sanguramath, RA, Shenhar, R, Eisen, M & Milstein, D 2022, 'Iron-catalysed ring-opening metathesis polymerization of olefins and mechanistic studies', Nature Catalysis, vol. 5, no. 6, pp. 494-502. https://doi.org/10.1038/s41929-022-00793-4

TY - JOUR

T1 - Iron-catalysed ring-opening metathesis polymerization of olefins and mechanistic studies

AU - Takebayashi, Satoshi

AU - Iron, Mark A.

AU - Feller, Moran

AU - Rivada-Wheelaghan, Orestes

AU - Leitus, Gregory

AU - Diskin-Posner, Yael

AU - Shimon, Linda J.W.

AU - Avram, Liat

AU - Carmieli, Raanan

AU - Wolf, Sharon G.

AU - Cohen-Ofri, Ilit

AU - Sanguramath, Rajashekharayya A.

AU - Shenhar, Roy

AU - Eisen, Moris

AU - Milstein, David

N1 - Funding Information: This research was supported by the Israel Science Foundation (1721/13, D.M.) and the Japan Society for the Promotion of Science (18K14230, S.T.). Electron microscopy studies were supported in part by the Irving and Cherna Moskowitz Center for Nano and Bio-Nano Imaging at the Weizmann Institute of Science. This work was supported by Okinawa Institute of Science and Technology Graduate University instrumental analysis and engineering sections. S.T. thanks M. C. Roy for the assistance with solid-state NMR measurement. D.M. holds the Israel Matz Professorial Chair. All data are provided in the Supplementary Information. This manuscript is dedicated to the memory of Professor Robert H. Grubbs. Publisher Copyright: © 2022, The Author(s), under exclusive licence to Springer Nature Limited.

PY - 2022/6

Y1 - 2022/6

N2 - The olefin metathesis reaction is among the most widely applicable catalytic reactions for carbon–carbon double bond formation. Currently, Mo– and Ru–carbene catalysts are the most common choices for this reaction. It has been suggested that an iron-based catalyst would be a desirable economical and biocompatible substitute of the Ru catalysts; however, practical solutions in this regard are still lacking. Here, we report the discovery and mechanistic studies of three-coordinate iron(II) catalysts for ring-opening metathesis polymerization of olefins. Remarkably, their reactivity enabled the formation of polynorbornene with stereoregularity and high molecular weight (>107 g mol–1). The polymerization in the presence of styrene revealed cross metathesis reactivity with iron catalysts. Mechanistic studies suggest the possible role of metal–ligand cooperation in formation of the productive catalyst. This work opens the door to the development of iron complexes that can be economical and biocompatible catalysts for olefin metathesis reactions. [Figure not available: see fulltext.]

AB - The olefin metathesis reaction is among the most widely applicable catalytic reactions for carbon–carbon double bond formation. Currently, Mo– and Ru–carbene catalysts are the most common choices for this reaction. It has been suggested that an iron-based catalyst would be a desirable economical and biocompatible substitute of the Ru catalysts; however, practical solutions in this regard are still lacking. Here, we report the discovery and mechanistic studies of three-coordinate iron(II) catalysts for ring-opening metathesis polymerization of olefins. Remarkably, their reactivity enabled the formation of polynorbornene with stereoregularity and high molecular weight (>107 g mol–1). The polymerization in the presence of styrene revealed cross metathesis reactivity with iron catalysts. Mechanistic studies suggest the possible role of metal–ligand cooperation in formation of the productive catalyst. This work opens the door to the development of iron complexes that can be economical and biocompatible catalysts for olefin metathesis reactions. [Figure not available: see fulltext.]

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DO - 10.1038/s41929-022-00793-4

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VL - 5

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EP - 502

JO - Nature Catalysis

JF - Nature Catalysis

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ER -

Iron-catalysed ring-opening metathesis polymerization of olefins and mechanistic studies

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