2005
DOI: 10.1021/ma051224a
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DFT Investigation of the Single-Center, Two-State Model for the Broken Rate Order of Transition Metal Catalyzed Olefin Polymerization

Abstract: Density functional calculations have been performed on different conformers and isomers of the propyl group in alkyl cations [L2Zr−Pr]+ (L = Cp, Cp*; Pr = n-propyl), corresponding to two catalysts with different observed rate orders (n) for ethylene polymerization, to explore the single-center, two-state kinetic model for olefin polymerization. For L = Cp (n ≈ 1), the β-agostic conformer is found to be the most stable structure and also the most reactive with respect to ethylene coordination, which is commensu… Show more

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Cited by 25 publications
(13 citation statements)
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“…This choice was inspired by the ability of a propyl ligand to form the most important agostic interactions (see, for example, ref. 148) and undergo model β‐hydride elimination reactions in a realistic environment 149…”
Section: Computational Detailsmentioning
confidence: 99%
“…This choice was inspired by the ability of a propyl ligand to form the most important agostic interactions (see, for example, ref. 148) and undergo model β‐hydride elimination reactions in a realistic environment 149…”
Section: Computational Detailsmentioning
confidence: 99%
“…A Zr-alkyl structure featuring a pronounced b-C-H agostic interaction with the metal atom has been established as the undisputed resting state in computational investigations of olefin polymerization using zirconocene catalysts [30,123]. This does not only imply that the b-agostic structures are the most stable among the possible alkene-free conformers, but also that the latter are more stable, in terms of free energy, than the corresponding (alkene)metal-alkyl complexes.…”
Section: [{H 2 C(cp) 2 }Zr-pr] + (Pr = N-propyl)mentioning
confidence: 99%
“…The c-agostic conformer which is the primary product of insertion [30,123] is only slightly higher in energy (2.2 kcal/mol) and can also easily rearrange to the b-agostic resting state (via a TS at 4.3 kcal/ mol). The three a-agostic conformers are less stable (8.2-10.3 kcal/mol above the resting state).…”
Section: [H 2 C(cp) 2 Zr-i Bu] + ( I Bu = Iso-butyl)mentioning
confidence: 99%
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“…Its application is relatively recent, but the importance of concentration effects had been previously recognized by several authors, which introduced them in a variety of ways. We review here some of these applications, which may be viewed as implicit microkinetic modeling (Jensen, Koley, Jagadeesh, & Thiel, 2005;Muñoz-Molina et al, 2011).…”
Section: Concentration Effects Without Microkinetic Modelingmentioning
confidence: 99%