Syntheses of Rare-Earth Metal Alkyl Complexes Bearing a Dianionic α-Iminopyridyl Ligand and Their Catalytic Activities toward Polymerization of 2-Vinylpyridine

Zhang, Xiuli; Zhou, Shuangliu; Wang, Donghan; Zhang, Lijun; Wei, Yun; Zhu, Xiancui; Cui, Peng; Luo, Gen; Wang, Shaowu

doi:10.1021/acs.organomet.1c00470

Cited by 9 publications

(4 citation statements)

References 73 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Wang et al. reported that rare‐earth metal alkyl complexes 46 – 51 bearing a dianionic α‐iminopyridyl ligand exhibited good catalytic activities (∼400 h −1 ) toward polymerization of 2‐VP with high iso‐selectivity ( P m ∼0.96) (Scheme 5, Table 4, Runs 5–10) [20] . Luo et al.…”

Section: Stereoselective Polymerization Of 2‐vinylpyridinementioning

confidence: 99%

“…[19] Wang et al reported that rare-earth metal alkyl complexes 46-51 bearing a dianionic α-iminopyridyl ligand exhibited good catalytic activities (~400 h À 1 ) toward polymerization of 2-VP with high isoselectivity (P m ~0.96) (Scheme 5, Table 4, Runs 5-10). [20] ). [21] In 2018, Mu's group [22] reported the catalytic performance of diketiminato rare earth metal complexes 58-63 for 2-VP polymerization (Scheme 6).…”

Section: Runmentioning

confidence: 99%

See 1 more Smart Citation

Stereoselective Polymerization of Aromatic Vinyl Polar Monomers

2023

Eur J Inorg Chem

View full text Add to dashboard Cite

Polar vinyl polymers, a class of polymers with polar groups as side chains, have significant advantages over conventional nonpolar polyolefin materials in terms of viscosity, toughness, interfacial properties (dyeability and printability), and compatibility with solvents or other polymers. Among them, aromatic polar vinyl polymers are of interest because of their good heat resistance properties. In addition, stereoselective polymerization of aromatic polar vinyl monomers has been rapidly developed because the steric structure of the polymer has a significant impact on its physical properties. In this paper, we review the research progress of stereoselective polymerization catalysts for aromatic polar vinyl monomers in recent years, discuss in detail the influence of ligand structure, electronic effect of substituents, spatial site resistance effect, central rare earth metal species and polymerization solvents on the activity and stereoselectivity of polymerization reactions, and explore the possible mechanism of polymerization reaction.

show abstract

Section: Stereoselective Polymerization Of 2‐vinylpyridinementioning

confidence: 99%

Section: Runmentioning

confidence: 99%

Stereoselective Polymerization of Aromatic Vinyl Polar Monomers

2023

Eur J Inorg Chem

View full text Add to dashboard Cite

show abstract

“…To be noted, this fascinating copolymerization provides an ideal model to computationally simulate the competitive insertion behaviors of polar and nonpolar olefins and to elucidate the origins of specific regio- and stereoselectivity. As part of our ongoing endeavors in the mechanistic understanding of rare-earth catalysis, ,, we performed here a detailed mechanistic investigation on the model reaction of co-syndiospecific alternating copolymerization of anisylpropylene (AP) and styrene catalyzed by C 5 Me 4 SiMe 3 -ligated scandium complex ( Sc-1 ) through DFT calculations (Figure c). By comparison of various possible insertion modes, a new amino-dissociated mechanism was proposed for AP insertion at chain initiation.…”

Section: Introductionmentioning

confidence: 99%

Unveiling the Detailed Mechanism and Origins of Chemo-, Regio-, and Stereoselectivity of Rare-Earth Catalyzed Alternating Copolymerization of Polar and Nonpolar Olefins

Zhang,

Xue,

Shi

et al. 2024

Inorg. Chem.

Self Cite

View full text Add to dashboard Cite

The direct copolymerization of polar and nonpolar olefins is of great interest and significance, as it is the most atomeconomical and straightforward strategy for the synthesis of functional polyolefin materials. Despite considerable efforts, the precise control of monomer-sequence and their regio-and stereochemistry is full of challenges, and the related mechanistic origins are still in their infancy to date. Herein, the mechanistic studies on the model reaction of Sc-catalyzed co-syndiospecific alternating copolymerization of anisylpropylene (AP) and styrene were performed by DFT calculations. The results suggest that the subtle balance between electronic and steric factors plays an important role during monomer insertions, and a new aminodissociated mechanism was proposed for AP insertion at chain initiation. AP insertion follows the 2,1-si-insertion pattern, which is mainly controlled by steric factors caused by the restricted MeO•••Sc interaction. As for styrene insertion, it prefers the 2,1-reinsertion manner and its regio-and stereoselectivities are influenced by steric repulsions between the inserting styrene and the polymer chain or the ligand. More interestingly, it is found that the alternating monomer-sequence is mainly determined by the "steric matching" principle, which is quantitatively expressed by the buried volume of the metal center of the preinserted species. The concept of steric pocket has been successfully applied to explain the different performances of several catalysts and other alternating copolymerization reactions. The insightful mechanistic findings and the quantitative steric pocket model present here are expected to promote rational design of new rare-earth catalysts for developing regio-, stereo-, and sequence-controlled copolymerization of specific polar and nonpolar olefins.

show abstract

“…In our previous work, the double deprotonation of morpholinyl-substituted 2-aminomethyl pyridine in the presence of rare-earth metal triamido/trialkyl complexes was a feasible way to anchor an α-iminopyridine moiety in the dianionic form with a novel μ- η 2 : σ 1 : κ 1 binding mode to the metal center . The absence of double deprotonation was observed if the morpholinyl group was replaced with a noncoordinating group, i.e., a tert -butyl group, emphasizing the key role of the coordinated morpholinyl moiety in the sequential deprotonation.…”

Section: Introductionmentioning

confidence: 99%

Ether/Thioether-Functionalized Dianionic α-Iminopyridine Rare-Earth Metal Amido Complexes and Their Catalytic Activity toward Hydrophosphination of Alkenes

et al. 2022

Self Cite

View full text Add to dashboard Cite

The double deprotonation of 2-aminomethyl pyridine by rare-earth metal triamido complexes was found to be an alternative strategy to anchor dianionic iminopyridine on rare-earth metal centers with the morpholinyl group previously. To verify the generality of the protocol with different appendant donor groups, reactions of [(Me 3 Si) 2 N] 3 RE(μ-Cl)Li(THF) 3 with ether/ thiotether-substituted 2-aminomethyl pyridine 2-(CH 3 DCH 2 CH 2 NHCH 2 )-6-R-C 5 H 3 N (D = O, R = H (1), Ph (2); D = S, R = H (3)) were performed, leading to the formation of ether/thioether-functionalized dianionic α-iminopyridine rare-earth metal amido complexes {μ-η 2 :σ 1 :κ 1 :κ 1 -2-[CH 3 ECH 2 CH 2 NCH]-6-R-C 5 H 3 N} 2 RE 2 [N(SiMe 3 ) 2 ] 2 (D = O, R = H, RE = Dy (4a), Y (4b), Er (4c), Yb (4d), Lu (4e), R = Ph, RE = Dy (5a), Y (5b), Er (5c), Lu (5d); D = S, R = H, RE = Y (6a), Er (6b), Lu ( 6c)). These results supported the ability of oxygen or sulfur coordination in promoting the double deprotonation of 2-aminomethyl pyridine to construct new iminopyridine rare-earth metal complexes in the dianionic form. Further examination of these rare-earth metal amido complexes displayed good catalytic activity for hydrophosphination of alkenes, affording anti-Markovnikov addition products under solvent-free conditions.

show abstract

Syntheses of Rare-Earth Metal Alkyl Complexes Bearing a Dianionic α-Iminopyridyl Ligand and Their Catalytic Activities toward Polymerization of 2-Vinylpyridine

Cited by 9 publications

References 73 publications

Stereoselective Polymerization of Aromatic Vinyl Polar Monomers

Stereoselective Polymerization of Aromatic Vinyl Polar Monomers

Unveiling the Detailed Mechanism and Origins of Chemo-, Regio-, and Stereoselectivity of Rare-Earth Catalyzed Alternating Copolymerization of Polar and Nonpolar Olefins

Ether/Thioether-Functionalized Dianionic α-Iminopyridine Rare-Earth Metal Amido Complexes and Their Catalytic Activity toward Hydrophosphination of Alkenes

Contact Info

Product

Resources

About