Application of the frontier molecular orbital theory to the interpretation of the Hammett correlation's

Henri‐Rousseau, Olivier; Texier, F.

doi:10.1021/ed055p437

Cited by 46 publications

(18 citation statements)

References 7 publications

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“…Henri-Rousseau et al [4] have proposed that a positive charge on the reactant will lower the energy of the LUMO and a negative charge will increase the energy of the HOMO. This hypothesis can be tested with reference to the present system.…”

Section: Resultsmentioning

confidence: 99%

“…Since that time there has been rapid scientific and technological development of catalysis for olefin polymerisation and many recent reports and reviews of such progress have been published [1][2][3][4][5][6][7][8][9][10][11][12][13]. While many different types of metal complexes have been shown to act as catalysts in polymerisation, the metallocenes have been found to be particularly useful.…”

Section: Introductionmentioning

confidence: 99%

“…The charge distribution in a chemical system has a definite effect on chemical reaction. The rate or equilibrium constants for reactions of the substituted and the unsubstituted compounds correlate with partial charge stabilisation following the Hammett equation [4,5]. However, this concept does not provide an explanation of regioselectivity and reactivity [4].…”

Section: Introductionmentioning

confidence: 99%

“…The rate or equilibrium constants for reactions of the substituted and the unsubstituted compounds correlate with partial charge stabilisation following the Hammett equation [4,5]. However, this concept does not provide an explanation of regioselectivity and reactivity [4]. Henri-Rousseau and Texier [4] correlated the activation energy of a reaction with the charge on the reactants by frontier molecular orbital theory.…”

Section: Introductionmentioning

confidence: 99%

“…However, this concept does not provide an explanation of regioselectivity and reactivity [4]. Henri-Rousseau and Texier [4] correlated the activation energy of a reaction with the charge on the reactants by frontier molecular orbital theory. There are also extensive investigations on the relationship between charge distribution and reactivity for polymerisation [6].…”

Section: Introductionmentioning

confidence: 99%

See 4 more Smart Citations

Correlation between regioselectivity and site charge in propene polymerisation catalysed by metallocene

Liu

Drew

2009

Struct Chem

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The reactions of propene with [Zr(cyclopentadienyl) 2 Me] ? have been investigated using density functional theory in order to study the correlation between regioselectivity and site charge in propene polymerisation. The reaction paths of the 1,2 and 2,1 additions of the methyl group to propene have been established. The geometries and energies of the reactants, transition states and products have been obtained using both PBEPBE/LANL2DZ and B3LYP/ LANL2DZ methodologies. The results with both density functionals show that the activation energy for 1,2-insertion is lower than that for 2,1-insertion (Fig. 5) and this is consistent with the experiment results. Also for both density functionals, the difference of the thermal dynamic driving forces between the 2,1 product named 2-21 and the 1,2 product named 2-12 is significantly lower than the difference between the energy barriers. It is noted that in the reactants, the Mulliken partial charge on the central carbon atom C2 is positive and it can be concluded that 1,2-insertion is favoured because it can proceed via a cationic reaction.

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Section: Resultsmentioning

confidence: 99%