Rational Design of Aldimine Imidazolidin-2-imine/Guanidine Nickel Catalysts for Norbornene (Co)Polymerizations with Enhanced Catalytic Performance

Mingyuan Li; Zhengguo Cai; Moris S. Eisen

doi:10.1016/j.jcat.2023.02.015

Rational Design of Aldimine Imidazolidin-2-imine/Guanidine Nickel Catalysts for Norbornene (Co)Polymerizations with Enhanced Catalytic Performance

Mingyuan Li, Zhengguo Cai^*, Moris S. Eisen^*

^*Corresponding author for this work

Chemistry

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

1 Scopus citations

Abstract

The development of late transition metal catalysts bearing novel ligand platforms is a convenient pathway to obtain prospective systems with enhanced catalytic performance, however, it remains a challenge in the field of olefin (co)polymerizations. In this contribution, a new family of [N,N]-type of bidentate aldimine imidazolidin-2-imine/guanidine ligands and their nickel complexes Ni1–Ni7 bearing a distinct six-membered chelate ring were successfully synthesized, and characterized. All of the nickel catalysts were active for norbornene polymerization with high activity of up to 7.44 × 105 g mol–1 h−1. These catalysts also copolymerized norbornene and 1-alkenes (1-dodecene and 1-octadecene) while keeping high activities to produce various norbornene-based high-molecular-weight (Mn = 5.75–36.0 kg mol−1) cyclic olefin copolymers (COCs) with adjustable 1-alkene incorporations (1.44–13.30 mol%) and a wide range of Tg values (102.2–271.4 °C). Moreover, with the decoration of bulky N-aryl substituents, these nickel catalysts exhibited strong tolerance towards polar monomer to promote the direct copolymerization of norbornene and methyl 10-undecenoate with high activity (up to 9.88 × 104 g mol–1 h−1), and furnished polar functionalized COCs with a high molecular weight (Mn up to 72.4 kg mol−1) and reasonable polar monomer incorporations (0.19–0.45 mol%). These nickel complexes are rare examples and also promising candidates as catalysts for the efficient synthesis of various COCs.

Original language	English
Journal	Journal of Catalysis
Volume	420
DOIs	https://doi.org/10.1016/j.jcat.2023.02.015
State	Published - 1 Apr 2023

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title = "Rational Design of Aldimine Imidazolidin-2-imine/Guanidine Nickel Catalysts for Norbornene (Co)Polymerizations with Enhanced Catalytic Performance",

abstract = "The development of late transition metal catalysts bearing novel ligand platforms is a convenient pathway to obtain prospective systems with enhanced catalytic performance, however, it remains a challenge in the field of olefin (co)polymerizations. In this contribution, a new family of [N,N]-type of bidentate aldimine imidazolidin-2-imine/guanidine ligands and their nickel complexes Ni1–Ni7 bearing a distinct six-membered chelate ring were successfully synthesized, and characterized. All of the nickel catalysts were active for norbornene polymerization with high activity of up to 7.44 × 105 g mol–1 h−1. These catalysts also copolymerized norbornene and 1-alkenes (1-dodecene and 1-octadecene) while keeping high activities to produce various norbornene-based high-molecular-weight (Mn = 5.75–36.0 kg mol−1) cyclic olefin copolymers (COCs) with adjustable 1-alkene incorporations (1.44–13.30 mol%) and a wide range of Tg values (102.2–271.4 °C). Moreover, with the decoration of bulky N-aryl substituents, these nickel catalysts exhibited strong tolerance towards polar monomer to promote the direct copolymerization of norbornene and methyl 10-undecenoate with high activity (up to 9.88 × 104 g mol–1 h−1), and furnished polar functionalized COCs with a high molecular weight (Mn up to 72.4 kg mol−1) and reasonable polar monomer incorporations (0.19–0.45 mol%). These nickel complexes are rare examples and also promising candidates as catalysts for the efficient synthesis of various COCs.",

author = "Mingyuan Li and Zhengguo Cai and Eisen, {Moris S.}",

year = "2023",

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T1 - Rational Design of Aldimine Imidazolidin-2-imine/Guanidine Nickel Catalysts for Norbornene (Co)Polymerizations with Enhanced Catalytic Performance

AU - Li, Mingyuan

AU - Cai, Zhengguo

AU - Eisen, Moris S.

PY - 2023/4/1

Y1 - 2023/4/1

N2 - The development of late transition metal catalysts bearing novel ligand platforms is a convenient pathway to obtain prospective systems with enhanced catalytic performance, however, it remains a challenge in the field of olefin (co)polymerizations. In this contribution, a new family of [N,N]-type of bidentate aldimine imidazolidin-2-imine/guanidine ligands and their nickel complexes Ni1–Ni7 bearing a distinct six-membered chelate ring were successfully synthesized, and characterized. All of the nickel catalysts were active for norbornene polymerization with high activity of up to 7.44 × 105 g mol–1 h−1. These catalysts also copolymerized norbornene and 1-alkenes (1-dodecene and 1-octadecene) while keeping high activities to produce various norbornene-based high-molecular-weight (Mn = 5.75–36.0 kg mol−1) cyclic olefin copolymers (COCs) with adjustable 1-alkene incorporations (1.44–13.30 mol%) and a wide range of Tg values (102.2–271.4 °C). Moreover, with the decoration of bulky N-aryl substituents, these nickel catalysts exhibited strong tolerance towards polar monomer to promote the direct copolymerization of norbornene and methyl 10-undecenoate with high activity (up to 9.88 × 104 g mol–1 h−1), and furnished polar functionalized COCs with a high molecular weight (Mn up to 72.4 kg mol−1) and reasonable polar monomer incorporations (0.19–0.45 mol%). These nickel complexes are rare examples and also promising candidates as catalysts for the efficient synthesis of various COCs.

AB - The development of late transition metal catalysts bearing novel ligand platforms is a convenient pathway to obtain prospective systems with enhanced catalytic performance, however, it remains a challenge in the field of olefin (co)polymerizations. In this contribution, a new family of [N,N]-type of bidentate aldimine imidazolidin-2-imine/guanidine ligands and their nickel complexes Ni1–Ni7 bearing a distinct six-membered chelate ring were successfully synthesized, and characterized. All of the nickel catalysts were active for norbornene polymerization with high activity of up to 7.44 × 105 g mol–1 h−1. These catalysts also copolymerized norbornene and 1-alkenes (1-dodecene and 1-octadecene) while keeping high activities to produce various norbornene-based high-molecular-weight (Mn = 5.75–36.0 kg mol−1) cyclic olefin copolymers (COCs) with adjustable 1-alkene incorporations (1.44–13.30 mol%) and a wide range of Tg values (102.2–271.4 °C). Moreover, with the decoration of bulky N-aryl substituents, these nickel catalysts exhibited strong tolerance towards polar monomer to promote the direct copolymerization of norbornene and methyl 10-undecenoate with high activity (up to 9.88 × 104 g mol–1 h−1), and furnished polar functionalized COCs with a high molecular weight (Mn up to 72.4 kg mol−1) and reasonable polar monomer incorporations (0.19–0.45 mol%). These nickel complexes are rare examples and also promising candidates as catalysts for the efficient synthesis of various COCs.

U2 - 10.1016/j.jcat.2023.02.015

DO - 10.1016/j.jcat.2023.02.015

M3 - 文章

SN - 0021-9517

VL - 420

JO - Journal of Catalysis

JF - Journal of Catalysis

ER -

Rational Design of Aldimine Imidazolidin-2-imine/Guanidine Nickel Catalysts for Norbornene (Co)Polymerizations with Enhanced Catalytic Performance

Abstract

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