2021
DOI: 10.1002/asia.202100193
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Polymerization via Insertion of Ethylene into Al−C bond under Mild Conditions: Mechanistic Studies on the Promotion Exerted by a Catalytic Amount of Cationic Gadolinium Metallocene

Abstract: The cationic gadolinium metallocene [(C 5 Me 5 ) 2 Gd][B(C 6 F 5 ) 4 ], when combined with an excess amount of Al( i Bu) 3 , efficiently produces polyethylene at 80°C under 0.8 MPa pressure of ethylene. After quenching, the resulting polyethylene has ethyl group at one end and isobutyl group at the other terminal. Because no Gd-alkyl species appears to be involved, a mechanism with conventional coordinative chain transfer polymerization (CCTP) is not feasible. Density functional theory (DFT) analyses indicate … Show more

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Cited by 5 publications
(11 citation statements)
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“…As indicated in the introduction section, many previous studies have suggested displacement of the counter anion during polymerizations to enhance catalysis [25–38] . In the previous DFT analysis of the polymerization of ethylene, it was found that the [B(C 6 F 5 ) 4 ] − exists in the vicinity of the [Cp* 2 Gd] + and interacts with the [Cp* 2 Gd] + , but it is not directly involved in the monomer insertion reaction (Figure 1(b)) [18] . Our preliminary molecular dynamics simulation suggests that other species such as Al( i Bu) 3 and monomers in situ could assist the [B(C 6 F 5 ) 4 ] − unit to dissociate from Gd, and it was also observed that a butadiene monomer has a stronger dissociation‐assisting effect than an ethylene monomer [49] .…”
Section: Resultsmentioning
confidence: 96%
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“…As indicated in the introduction section, many previous studies have suggested displacement of the counter anion during polymerizations to enhance catalysis [25–38] . In the previous DFT analysis of the polymerization of ethylene, it was found that the [B(C 6 F 5 ) 4 ] − exists in the vicinity of the [Cp* 2 Gd] + and interacts with the [Cp* 2 Gd] + , but it is not directly involved in the monomer insertion reaction (Figure 1(b)) [18] . Our preliminary molecular dynamics simulation suggests that other species such as Al( i Bu) 3 and monomers in situ could assist the [B(C 6 F 5 ) 4 ] − unit to dissociate from Gd, and it was also observed that a butadiene monomer has a stronger dissociation‐assisting effect than an ethylene monomer [49] .…”
Section: Resultsmentioning
confidence: 96%
“…We investigate the mechanism of butadiene polymerization with adopting the previously estimated active species without the [B(C 6 F 5 ) 4 ] − (Figure 2). [18] And, we analyzed the stereoselective polymerization of 1,3‐butadiene based on that mechanism.…”
Section: Resultsmentioning
confidence: 99%
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