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Catalysts
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Rare Earth Complexes as Polymerization Catalysts
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Rare Earth Complexes as Polymerization Catalysts

A special issue of Catalysts (ISSN 2073-4344). This special issue belongs to the section "Catalytic Materials".

Deadline for manuscript submissions: closed (30 April 2020) | Viewed by 6733

Special Issue Editor

Dr. Fanny Bonnet

E-Mail Website
Guest Editor
Unité Matériaux et Transformations (UMET), UMR 8207, University of Lille, 59655 Villeneuve d’Ascq, France
Interests: Rare earth complexes; Polymerization catalysis; Ring Opening Polymerization (ROP); Reactive extrusion

Special Issue Information

Dear Colleagues,

The development of rare earth chemistry has witnessed spectacular growth in the last decades, where the design and application of complexes as polymerization catalysts has occupied an especially important place. Rare earth catalysts are nowadays widely involved in the field of coordination polymerization as they can produce high added-value stereoregular polymers or copolymers. In that frame, the design of well-defined ligands in order to tune the activity or selectivity of the polymerization catalysts plays a key role. Rare earth polymerization catalysts were first mainly dominated by metallocene complexes, before the more recent development of non-Cp, post-metallocene systems. The emergence of undercoordinated cationic catalytic species was also a breakthrough in the field, leading to extremely active and selective systems towards olefins and dienes. More recently, in a context of sustainable chemistry, many efforts have been made to develop ring opening polymerisation (ROP) catalysts of cyclic esters to produce various biodegradable polymers. The present Special Issue “Rare Earth Complexes as Polymerization Catalysts” aims at reflecting the recent advances in that research field. Submissions are welcome in the form of original research papers or short reviews that reflect the state of the research in the field of rare earth polymerization catalysts on the following topics: Stereoselective rare earth (co-)polymerization catalysts of olefins and/or conjugated dienes, ring opening polymerization (ROP) of cyclic esters, polymerization mechanisms involving rare earth catalysts, and computational calculations on rare earth polymerization catalytic systems.

Dr. Fanny Bonnet
Guest Editor

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Catalysts is an international peer-reviewed open access monthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2700 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • Rare earth
  • Organometallic chemistry
  • Coordination-insertion polymerization
  • Stereoselective (co-)polymerization
  • (co-)Polymerization of olefins and dienes
  • Ring opening polymerization
  • DFT calculations

Published Papers (2 papers)

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Research

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10 pages, 1701 KiB  
Article
Rationalizing the Reactivity of Mixed Allyl Rare-Earth Borohydride Complexes with DFT Studies
by Sami Fadlallah, Jashvini Jothieswaran, Iker Del Rosal, Laurent Maron, Fanny Bonnet and Marc Visseaux
Catalysts 2020, 10(8), 820; https://doi.org/10.3390/catal10080820 - 22 Jul 2020
Cited by 8 | Viewed by 2116
Abstract
The reactivity of rare-earth complexes RE(BH4)2(C3H5)(THF)x (RE = La, Nd, Sm, Y, Sc) toward the Ring-Opening Polymerization (ROP) of ε-caprolactone (ε-CL) was rationalized by Density Functional Theory (DFT) calculations. Even if the polymerization reaction [...] Read more.
The reactivity of rare-earth complexes RE(BH4)2(C3H5)(THF)x (RE = La, Nd, Sm, Y, Sc) toward the Ring-Opening Polymerization (ROP) of ε-caprolactone (ε-CL) was rationalized by Density Functional Theory (DFT) calculations. Even if the polymerization reaction can be initiated by both RE-(BH4) and RE-allyl bonds, experimental investigations have shown that the initiation via the borohydride ligand was favored, as no allyl group could be detected at the chain-end of the resulting polymers. DFT studies could confirm these observations, as it was highlighted that even if the activation barriers are both accessible, the allyl group is not active for the ROP of ε-CL due to the formation of a highly stable intermediate that disfavors the subsequent ring-opening. Full article
(This article belongs to the Special Issue Rare Earth Complexes as Polymerization Catalysts)
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Review

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14 pages, 5657 KiB  
Review
Recent Advances in Rare Earth Complexes Containing N-Heterocyclic Carbenes: Synthesis, Reactivity, and Applications in Polymerization
by Yu Pan, Xinxin Jiang, Yat-Ming So, Ching Tat To and Gaohong He
Catalysts 2020, 10(1), 71; https://doi.org/10.3390/catal10010071 - 3 Jan 2020
Cited by 25 | Viewed by 4130
Abstract
N-heterocyclic carbenes (NHCs) are ubiquitous ancillary ligands employed in metal-catalyzed homogeneous reactions and polymerization reactions. Of significance is the use of NHCs as the supporting ligand in second- and third-generation Grubbs catalysts for their application in olefin metathesis and ring-opening metathesis polymerization. While [...] Read more.
N-heterocyclic carbenes (NHCs) are ubiquitous ancillary ligands employed in metal-catalyzed homogeneous reactions and polymerization reactions. Of significance is the use of NHCs as the supporting ligand in second- and third-generation Grubbs catalysts for their application in olefin metathesis and ring-opening metathesis polymerization. While the applications of transition metal catalysts ligated with NHCs in polymerization chemistry are well-documented, the use of analogous rare earth (Ln = Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu) catalysts in this area remains under-developed, despite the unique role of rare earth elements in regio- and stereo-specific (co)polymerization reactions. By using hetero-atom-tethered chelating NHCs and, more recently, the employment of other structurally related NHCs, NHC-ligated Ln complexes have proven to be promising and fruitful catalysts for selective polymerization reactions. This review summarizes the recent developments in the coordination chemistry of Ln complexes containing NHCs and their catalytic performance in polymerization. Full article
(This article belongs to the Special Issue Rare Earth Complexes as Polymerization Catalysts)
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