Center for Molecular Modeling - L. Hermosilla

On the Possibility of [1,5] Sigmatropic Shifts in Bicyclo[4.2.0]octa-2,4-dienes

michel — Sun, 30 Nov 2014 13:27:40 +0000

H. Goossens, J.M. Winne, S. Wouters, L. Hermosilla, P. J. De Clercq, M. Waroquier, V. Van Speybroeck, S. Catak

Journal of Organic Chemistry

80 (5) 2609-2620

2015

Abstract

The thermal equilibration of the methyl esters of endiandric acids D and E was subject to a computational study. An electrocyclic pathway via an electrocyclic ring opening followed by a ring flip and a subsequent electrocyclization proposed by Nicolaou [Chem. Soc. Rev. 2009], was computationally explored. The free energy barrier for this electrocyclic route was shown to be very close to the bicyclo[4.2.0]octa-2,4-diene reported by Huisgen [Tet. Lett. 1968]. Furthermore, the possibility of a [1,5] sigmatropic alkyl group shift of bicyclo[4.2.0]octa-2,4-diene systems at high temperatures was explored in a combined computational and experimental study. Calculated reaction barriers for a biradical-mediated stepwise [1,5] sigmatropic alkyl group shift were shown to be comparable with the reaction barriers for the bicyclo[4.1.0]hepta-2,4-diene (norcaradiene) walk rearrangement, whereas calculated reaction barriers for a concerted [1,5] sigmatropic alkyl group shift were found to be higher in energy. However, the stepwise pathway is suggested to only be feasible for appropriately substituted compounds. Experiments conducted on a deuterated analogous diol derivative confirmed the calculated (large) differences in barriers between electrocyclic and sigmatropic pathways.

DOI

http://dx.doi.org/10.1021/jo5027639

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15_JOC_xxxx_HGoossens.pdf

Competitive Reactions of Organophosphorus Radicals on Coke Surfaces

wim — Wed, 12 Oct 2011 13:56:17 +0000

S. Catak, K. Hemelsoet, L. Hermosilla, M. Waroquier, V. Van Speybroeck

Chemistry - A European Journal

17 (43), 12027–12036

2011

Abstract

The efficacy of organophosphorus radicals as anticoking agents was subjected to a computational study in which a representative set of radicals derived from industrially relevant organophosphorus additives was used to explore competitive reaction pathways on the graphene-like coke surface formed during thermal cracking. The aim was to investigate the nature of the competing reactions of different organophosphorus radicals on coke surfaces, and elucidate their mode of attack and inhibiting effect on the forming coke layer by use of contemporary computational methods. Density functional calculations on benzene and a larger polyaromatic hydrocarbon, namely, ovalene, showed that organophosphorus radicals have a high propensity to add to the periphery of the coke surface, inhibiting methyl radical induced hydrogen abstraction, which is known to be a key step in coke growth. Low addition barriers reported for a phosphatidyl radical suggest competitive aptitude against coke formation. Moreover, organophosphorus additives bearing aromatic substituents, which were shown to interact with the coke surface through dispersive π–π stacking interactions, are suggested to play a nontrivial role in hindering further stacking among coke surfaces. This may be the underlying rationale behind experimental observation of softer coke in the presence of organophosphorus radicals. The ultimate goal is to provide information that will be useful in building single-event microkinetic models. This study presents pertinent information on potential reactions that could be taken up in these models.

DOI

http://dx.doi.org/10.1002/chem.201100712

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cover chem eur j.17.43.pdf

11 chem eur j 17(43)12027 catak.pdf

Kinetic and Mechanistic Study on p-Quinodimethane Formation in the Sulfinyl Precursor Route for the Polymerization of Poly(p-phenylenevinylene) (PPV)

wim — Tue, 13 Sep 2011 12:01:44 +0000

L. Hermosilla, S. Catak, V. Van Speybroeck, M. Waroquier, J. Vandenbergh, F. Motmans, P. Adriaensens, L. Lutsen, T. Cleij, D. Vanderzande

Macromolecules

43 (18), 7424–7433

2010

Abstract

The kinetics of p-quinodimethane formation in the sulfinyl precursor route for the poly(p-phenylenevinylene) (PPV) polymerization was studied using stop-flow UV−vis spectroscopy and theoretical first principle calculations. Different sulfinyl monomers were studied by means of quantitative kinetic experiments regarding the p-quinodimethane formation in 2-butanol. The influence of the solvent, the nature of the aromatic moiety, and the substituents on the phenyl core was analyzed by means of qualitative experiments. Quantitative measurements, using pseudo-first-order reaction conditions, were performed in order to assess the effect of the polarizer and the leaving group on the reaction rates. To obtain additional fundamental insight into the pathway leading to p-quinodimethane formation, density functional theory calculations were performed and subsequent reaction rate coefficients were determined from a theoretical point of view, enabling a profound comparison with experiment. From all these data, an E2 mechanism is proposed for the p-quinodimethane formation in the sulfinyl precursor route.

DOI

http://dx.doi.org/10.1021/ma1013012

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10 macromolecules 43, 7424 hermosilla.pdf

DFT insight into the polymerization mechanism of conjugated electroluminescent polymer PPV

catak — Wed, 18 Jan 2012 17:05:17 +0000

S. Catak, L. Hermosilla, B. Champagne, D. Vanderzande, M. Waroquier, V. Van Speybroeck

WP2/5

Poster

Conference / event / venue

Belgium Science Policy (Belspo)–Annual Meeting for Interuniversity Attraction Poles (IUAP)

Leuven, Belgium

Monday, 21 November, 2011 to Tuesday, 22 November, 2011

Abstract (private)

2011 IAP WP2_5.pdf

Conference reference

Annual Meeting for Interuniversity Attraction Poles (IUAP) 2011

DFT insight into the mechanism towards the synthesis of the conjugated electroluminescent polymer PPV

wim — Mon, 17 Oct 2011 14:25:00 +0000

L. Hermosilla, V. Van Speybroeck, M. Waroquier, D. Vanderzande

Poster

Conference / event / venue

IAP-PAI P6/27 Annual Meeting

Leuven, Belgium

Monday, 14 December, 2009 to Tuesday, 15 December, 2009