β-Lactone synthesis from epoxide and CO: Reaction mechanism revisited

A. Stirling, Marcella Iannuzzi, Michele Parrinello, Ferenc Molnar, Volker Bernhart, Gerrit A. Luinstra

Research output: Contribution to journalArticle

39 Citations (Scopus)

Abstract

The formation of β-lactone from epoxide and CO catalyzed by CoCO 4- has been studied using a novel ab initio molecular dynamics approach. Employing the so-called metadynamics methodology, we show that it is possible to unravel the reaction mechanism of the catalyzed lactone formation in a fairly unbiased way. We were able to reproduce all the elementary steps within relatively short simulation time: the epoxide opening, the CO insertion, the CO addition to the Co site, the lactone ring formation, and the product dissociation, as obtained in previous static calculations. In addition, the simulations revealed that the lowest energy path goes through a stable intermediate featuring a metalla-oxo-furanyl ring. The simulations also indicated a new, higher energy path, in which the lactone ring formation precedes the CO uptake of the Co center. We show that this route becomes competitive when the Lewis acid attached to the lactone oxygen is softer.

Original languageEnglish
Pages (from-to)2533-2537
Number of pages5
JournalOrganometallics
Volume24
Issue number10
DOIs
Publication statusPublished - May 9 2005

Fingerprint

epoxy compounds
Epoxy Compounds
Lactones
Carbon Monoxide
synthesis
rings
simulation
Lewis Acids
insertion
routes
dissociation
methodology
Molecular dynamics
molecular dynamics
acids
energy
Oxygen
oxygen
products

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

Cite this

Stirling, A., Iannuzzi, M., Parrinello, M., Molnar, F., Bernhart, V., & Luinstra, G. A. (2005). β-Lactone synthesis from epoxide and CO: Reaction mechanism revisited. Organometallics, 24(10), 2533-2537. https://doi.org/10.1021/om0502234

β-Lactone synthesis from epoxide and CO : Reaction mechanism revisited. / Stirling, A.; Iannuzzi, Marcella; Parrinello, Michele; Molnar, Ferenc; Bernhart, Volker; Luinstra, Gerrit A.

In: Organometallics, Vol. 24, No. 10, 09.05.2005, p. 2533-2537.

Research output: Contribution to journalArticle

Stirling, A, Iannuzzi, M, Parrinello, M, Molnar, F, Bernhart, V & Luinstra, GA 2005, 'β-Lactone synthesis from epoxide and CO: Reaction mechanism revisited', Organometallics, vol. 24, no. 10, pp. 2533-2537. https://doi.org/10.1021/om0502234
Stirling A, Iannuzzi M, Parrinello M, Molnar F, Bernhart V, Luinstra GA. β-Lactone synthesis from epoxide and CO: Reaction mechanism revisited. Organometallics. 2005 May 9;24(10):2533-2537. https://doi.org/10.1021/om0502234
Stirling, A. ; Iannuzzi, Marcella ; Parrinello, Michele ; Molnar, Ferenc ; Bernhart, Volker ; Luinstra, Gerrit A. / β-Lactone synthesis from epoxide and CO : Reaction mechanism revisited. In: Organometallics. 2005 ; Vol. 24, No. 10. pp. 2533-2537.
@article{1e133e9c42114933947fd24e6fd4df21,
title = "β-Lactone synthesis from epoxide and CO: Reaction mechanism revisited",
abstract = "The formation of β-lactone from epoxide and CO catalyzed by CoCO 4- has been studied using a novel ab initio molecular dynamics approach. Employing the so-called metadynamics methodology, we show that it is possible to unravel the reaction mechanism of the catalyzed lactone formation in a fairly unbiased way. We were able to reproduce all the elementary steps within relatively short simulation time: the epoxide opening, the CO insertion, the CO addition to the Co site, the lactone ring formation, and the product dissociation, as obtained in previous static calculations. In addition, the simulations revealed that the lowest energy path goes through a stable intermediate featuring a metalla-oxo-furanyl ring. The simulations also indicated a new, higher energy path, in which the lactone ring formation precedes the CO uptake of the Co center. We show that this route becomes competitive when the Lewis acid attached to the lactone oxygen is softer.",
author = "A. Stirling and Marcella Iannuzzi and Michele Parrinello and Ferenc Molnar and Volker Bernhart and Luinstra, {Gerrit A.}",
year = "2005",
month = "5",
day = "9",
doi = "10.1021/om0502234",
language = "English",
volume = "24",
pages = "2533--2537",
journal = "Organometallics",
issn = "0276-7333",
publisher = "American Chemical Society",
number = "10",

}

TY - JOUR

T1 - β-Lactone synthesis from epoxide and CO

T2 - Reaction mechanism revisited

AU - Stirling, A.

AU - Iannuzzi, Marcella

AU - Parrinello, Michele

AU - Molnar, Ferenc

AU - Bernhart, Volker

AU - Luinstra, Gerrit A.

PY - 2005/5/9

Y1 - 2005/5/9

N2 - The formation of β-lactone from epoxide and CO catalyzed by CoCO 4- has been studied using a novel ab initio molecular dynamics approach. Employing the so-called metadynamics methodology, we show that it is possible to unravel the reaction mechanism of the catalyzed lactone formation in a fairly unbiased way. We were able to reproduce all the elementary steps within relatively short simulation time: the epoxide opening, the CO insertion, the CO addition to the Co site, the lactone ring formation, and the product dissociation, as obtained in previous static calculations. In addition, the simulations revealed that the lowest energy path goes through a stable intermediate featuring a metalla-oxo-furanyl ring. The simulations also indicated a new, higher energy path, in which the lactone ring formation precedes the CO uptake of the Co center. We show that this route becomes competitive when the Lewis acid attached to the lactone oxygen is softer.

AB - The formation of β-lactone from epoxide and CO catalyzed by CoCO 4- has been studied using a novel ab initio molecular dynamics approach. Employing the so-called metadynamics methodology, we show that it is possible to unravel the reaction mechanism of the catalyzed lactone formation in a fairly unbiased way. We were able to reproduce all the elementary steps within relatively short simulation time: the epoxide opening, the CO insertion, the CO addition to the Co site, the lactone ring formation, and the product dissociation, as obtained in previous static calculations. In addition, the simulations revealed that the lowest energy path goes through a stable intermediate featuring a metalla-oxo-furanyl ring. The simulations also indicated a new, higher energy path, in which the lactone ring formation precedes the CO uptake of the Co center. We show that this route becomes competitive when the Lewis acid attached to the lactone oxygen is softer.

UR - http://www.scopus.com/inward/record.url?scp=18844406250&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=18844406250&partnerID=8YFLogxK

U2 - 10.1021/om0502234

DO - 10.1021/om0502234

M3 - Article

AN - SCOPUS:18844406250

VL - 24

SP - 2533

EP - 2537

JO - Organometallics

JF - Organometallics

SN - 0276-7333

IS - 10

ER -