1994
DOI: 10.1021/ja00095a034
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Ab Initio Molecular Dynamics Study of Metallocene-Catalyzed Ethylene Polymerization

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Cited by 121 publications
(82 citation statements)
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“…The results of the EHT analysis give two important hints: (i) the barrier for the insertion step is predicted to be low, in line with the theoretical data reported in the literature for the insertion of ethylene in a Ti-C bond; [19][20][21][22] (ii) no relevant differences for the insertion of butadiene into a Ti-butenyl bond and that of isoprene into a Ti-2-methylbutenyl bond have been found, confirming that the rate-determining step of homopolymerizations must be the coordination of the monomer to the active catalytic species. Indeed, only for that step have we found significantly different activation energies between butadiene and isoprene.…”
Section: Resultssupporting
confidence: 83%
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“…The results of the EHT analysis give two important hints: (i) the barrier for the insertion step is predicted to be low, in line with the theoretical data reported in the literature for the insertion of ethylene in a Ti-C bond; [19][20][21][22] (ii) no relevant differences for the insertion of butadiene into a Ti-butenyl bond and that of isoprene into a Ti-2-methylbutenyl bond have been found, confirming that the rate-determining step of homopolymerizations must be the coordination of the monomer to the active catalytic species. Indeed, only for that step have we found significantly different activation energies between butadiene and isoprene.…”
Section: Resultssupporting
confidence: 83%
“…As a result, no stationary points were found and the whole reaction appears to proceed downhill in energy. 17,19,20 However, experimental investigations would suggest a propagation barrier of 20-30 kJ/ mol. 24,25 That discordance might be attributed either to the fact that computations on bare cationic species may underestimate both the coordination and the insertion barriers or to specific interactions of the active species with solvent molecules, usually aromatic species, which may be coordinated onto the vacant site of the active species, so that their displacement by the incoming monomer will require energy.…”
Section: Introductionmentioning
confidence: 99%
“…The well defined molecular structure of metallocene catalysts and their analogues allows for thorough mechanistic investigations by theoretical methods, and several theoretical studies [5][6][7][8][9][10][11][12] have been conducted, using the bare cation, LL 0 MR + , as the model for the single site catalyst. However, recent findings indicate [13][14][15][16][17][18][19][20] that the anionic counterion plays an important role in the polymerization process.…”
Section: Introductionmentioning
confidence: 99%
“…4 Semiempirical methods have also been used The olefin insertion process into metallocene catamainly for the study of the olefin insertion process lyst systems has been widely investigated using in Ziegler-Natta and metallocene catalysts. 5 different theoretical approximations.…”
Section: Introductionmentioning
confidence: 99%