Dataset Information

Homo- and Copolymerization of Ethylene with Norbornene Catalyzed by Vanadium(III) Phosphine Complexes.

ABSTRACT: Herein, we report the homo- and co-polymerization of ethylene (E) with norbornene (NB) catalyzed by vanadium(III) phosphine complexes of the type VCl₃(PMe_nPh_3-n)₂ [n = 2 (1a), 1 (1b)] and VCl₃(PR₃)₂ [R = phenyl (Ph, 1c), cyclohexyl (Cy, 1d), tert-butyl (tBu, 1e)]. In the presence of Et₂AlCl and Cl₃CCOOEt (ETA), 1a-1e exhibit good activities for the polymerization of ethylene, affording linear, semicrystalline PEs with a melting temperature of approximately 130 °C. Mainly alternating copolymers with high comonomer incorporation were obtained in the E/NB copolymerization. A relationship was found between the electronic and steric properties of the phosphine ligands and the catalytic performance. Overall, the presence of electron-withdrawing ligand substituents increases the productivity, complexes with aryl phosphine (weaker ?-donor character) exhibiting a higher (co)polymerization initiation rate than those with alkyl phosphines (stronger ?-donor character). Steric effects also seem to play a key role since 1d and 1e, having large size phosphines (PCy₃ ? = 170° and PtBu₃ ? = 182°, respectively) are more active than 1a (PMe₂Ph ? = 122°). In this case, the larger size of PtBu₃ and PCy₃ likely compensates for their higher donor strength compared to PMe₂Ph.

SUBMITTER: Zanchin G

PROVIDER: S-EPMC6600629 | biostudies-literature | 2019 May

REPOSITORIES: biostudies-literature

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Homo- and Copolymerization of Ethylene with Norbornene Catalyzed by Vanadium(III) Phosphine Complexes.

Zanchin Giorgia G Gavezzoli Alessia A Bertini Fabio F Ricci Giovanni G Leone Giuseppe G

Molecules (Basel, Switzerland) 20190531 11

Herein, we report the homo- and co-polymerization of ethylene (E) with norbornene (NB) catalyzed by vanadium(III) phosphine complexes of the type VCl3(PMenPh3-n)2 [n = 2 (1a), 1 (1b)] and VCl3(PR3)2 [R = phenyl (Ph, 1c), cyclohexyl (Cy, 1d), tert-butyl (tBu, 1e)]. In the presence of Et2AlCl and Cl3CCOOEt (ETA), 1a-1e exhibit good activi ...[more]

PMID: 31159332

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Project description:Since the discovery of α-diimine catalysts in 1995, an extensive series of Brookhart-type complexes have shown their excellence in catalyzing ethylene polymerizations with remarkable activity and a high molecular weight. However, although this class of palladium complexes has proven proficiency in catalyzing ethylene copolymerization with various polar monomers, the α-diimine nickel catalysts have generally exhibited a much worse performance in these copolymerizations compared to their palladium counterparts. Recently, Brookhart et al. reported a notable exception, demonstrating that α-diimine nickel catalysts could catalyze the ethylene copolymerization with some vinylalkoxysilanes effectively, producing functionalized polyethylene incorporating trialkoxysilane (-Si(OR)3) groups. This breakthrough is significant since Pd-catalyzed copolymerizations are commercially less usable due to the high cost of palladium. Thus, the utilization of Ni, given its abundance in raw materials and cost-effectiveness, is a landmark in ethylene/polar vinyl monomer copolymerization. Inspired by these findings, we used density functional theory (DFT) calculations to investigate the mechanistic study of ethylene copolymerization with vinyltrimethoxysilane (VTMoS) catalyzed by Brookhart-type nickel catalysts, aiming to elucidate the molecular-level understanding of this unique reaction. Initially, the nickel complexes and cationic active species were optimized through DFT calculations. Subsequently, we explored the mechanisms including the chain initiation, chain propagation, and chain termination of ethylene homopolymerization and copolymerization catalyzed by Brookhart-type complexes. Finally, we conducted an energetic analysis of both the in-chain and chain-end of silane enchainment. It was found that chain initiation is the dominant step in the ethylene homopolymerization catalyzed by the α-diimine Ni complex. The 1,2- and 2,1-insertion of vinylalkoxysilane exhibit similar barriers, explaining the fact that both five-membered and four-membered chelates were identified experimentally. After the VTMoS insertion, the barriers of ethylene reinsertion become higher, indicating that this step is the rate-determining step, which could be attributed to the steric hindrance between the incoming ethylene and the bulky silane substrate. We have also reported the energetic analysis of the distribution of polar substrates. The dominant pathway of chain-end -Si(OR)3 incorporation is suggested as chain-walking → ring-opening → ethylene insertion, and the preference of chain-end -Si(OR)3 incorporation is primarily attributed to the steric repulsion between the pre-inserted silane group and the incoming ethylene molecule, reducing the likelihood of in-chain incorporation.

Dataset Information

Homo- and Copolymerization of Ethylene with Norbornene Catalyzed by Vanadium(III) Phosphine Complexes.

Publications

Homo- and Copolymerization of Ethylene with Norbornene Catalyzed by Vanadium(III) Phosphine Complexes.

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