Highly Active Iminopyridyl Iron-Based Catalysts for the Polymerization of Isoprene

Hashmi, Obaid-Hasan; Champouret, Yohan; Visseaux, Marc

Type de document :

Article dans une revue scientifique: Article original

DOI :

10.3390/molecules24173024

URL permanente :

http://hdl.handle.net/20.500.12210/13059

Titre :

Highly Active Iminopyridyl Iron-Based Catalysts for the Polymerization of Isoprene

Auteur(s) :

Hashmi, Obaid-Hasan [Auteur]
Unité de Catalyse et Chimie du Solide - UMR 8181 [UCCS]
Champouret, Yohan [Auteur]

Unité de Catalyse et Chimie du Solide - UMR 8181 [UCCS]
Visseaux, Marc [Auteur]

Unité de Catalyse et Chimie du Solide (UCCS) - UMR 8181
Unité de Catalyse et Chimie du Solide - UMR 8181 [UCCS]

Titre de la revue :

Molecules

Numéro :

Pagination :

3024

Date de publication :

2019-08

ISSN :

1420-3049

Discipline(s) HAL :

Chimie/Chimie de coordination

Résumé en anglais : [en]

A series of iminopyridyl-based ligands, 6-[(Ar)N=C(R)]-2-C6H5N [(Ar = 2,6-Me2-C6H3, R = Me (L1); Ar = 2,6-iPr2-C6H3, R = Me (L2); Ar = 2,6-Me2-C6H3, R = H (L3); Ar = 2,6-iPr2-C6H3, R = H (L4); Ar = 3,5-(CF3)2-C6H3, R = Me ...
Lire la suite >A series of iminopyridyl-based ligands, 6-[(Ar)N=C(R)]-2-C6H5N [(Ar = 2,6-Me2-C6H3, R = Me (L1); Ar = 2,6-iPr2-C6H3, R = Me (L2); Ar = 2,6-Me2-C6H3, R = H (L3); Ar = 2,6-iPr2-C6H3, R = H (L4); Ar = 3,5-(CF3)2-C6H3, R = Me (L5); Ar = C6F5, R = Me (L6)], and their corresponding iron (II) complexes were developed to investigate their application in the controlled coordinative polymerization of isoprene. The modulation of steric and electronic properties within this family of ligands/pre-catalysts has shown to influence the stereo-selectivity and activity of the polymerization of isoprene after activation. Upon activation with various co-catalysts such as AliBu3/[Ph3C][B(C6F5)4], AlEt3/[Ph3C][B(C6F5)4] or MAO, the resulting catalysts produced polyisoprenes with an excellent conversion (>99% of 500–5000 equiv.) within less than 1 h (TOF > 500 h−1) and having a variety of stereo-/regio-regularities. The presence of electron-donating and withdrawing groups drastically impacted the activity and the stereoselectivity of the catalysts during the course of the polymerization of isoprene. When activated with AliBu3/[Ph3C][B(C6F5)4], the complexes {6-[(2,6-Me2-C6H3)N=C(Me)]-2-C6H5N}FeCl2 (C1) and {6-[(2,6-iPr2-C6H3)N=C(Me)]-2-C6H5N}FeCl2 (C2) exhibited moderate trans-1,4 selectivity (>67%) while the iron-based systems bearing related aldiminopyridyl ligands {6-[(2,6-Me2-C6H3)N=C(H)]-2-C6H5N}FeCl2 (C3) and {6-[(2,6-iPr2-C6H3)N=C(H)]-2-C6H5N}FeCl2 (C4) were found to afford significant cis-1,4 selectivity at low temperature (>86% at −40 °C). On the other hand, the ternary {6-[(3,5-(CF3)2-C6H3)N=C(Me)]-2-C6H5N}FeCl2 (C5) or {6-[(C6F5)N=C(Me)]-2-C6H5N}FeCl2 (C6)/AliBu3/[Ph3C][B(C6F5)4] catalytic combinations showed exceptional activity for the polymerization of isoprene (TOF > 1,000,000 h−1), albeit providing less stereoselectivity.Lire moins >

Langue :

Anglais

Audience :

Internationale

Vulgarisation :

Non

Établissement(s) :

ENSCL
CNRS
Centrale Lille
Univ. Artois
Université de Lille

Collections :

Unité de Catalyse et Chimie du Solide (UCCS) - UMR 8181

Équipe(s) de recherche :

Méthodologie organométallique pour la catalyse homogène (MOCAH)

Date de dépôt :

2019-09-25T15:12:32Z
2019-10-09T08:42:09Z
2023-01-18T11:39:55Z

Fichiers

molecules-24-03024.pdf
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Ce document est diffusé sous licence Attribution 3.0 United States

Historique des modifications

Numéro de version	Lien	Date de modification
3	20.500.12210/13059*	2023-01-18T11:35:15Z
2	20.500.12210/13059.2	2019-10-09T08:41:21Z
1	20.500.12210/13059.1	2019-09-25T15:12:32Z

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