Mapping the potential energy surfaces for ring-closing metathesis reactions of prototypical dienes by electronic structure calculations

I.H. Hillier, S. Pandian, Jonathan Percy, M.A. Vincent

Research output: Contribution to journalArticle

29 Citations (Scopus)

Abstract

The potential energy surfaces for ring-closing metathesis reactions of a series of simple alpha,omega-dienes which lead to 5-10 membered ring products, have been explored using density functional theory methods. We have investigated both the conformational aspects of the hydrocarbon chain during the course of the reactions, as well as the stationary structures on the corresponding potential energy surfaces. Extensive conformational searches reveal that the reaction proceeds via the conformation that would be expected for the cycloalkene product, though most unexpectedly, cyclohexene forms via complexes in boat-like conformations. The M06-L density functional has been used to map out the potential energy surfaces, and has identified metallocyclobutane fragmentation as being generally the highest barrier along the pathway. The structural variations along the pathway have been discussed for the reactant hydrocarbons of differing chain length to identify points at which cyclisation events may begin to affect reaction rates. Our study provides an excellent starting point from which to begin to learn about the way RCM reaction outcomes are controlled by diene structure
LanguageEnglish
Pages1061-1072
Number of pages12
JournalDalton Transactions
Volume40
Issue number5
DOIs
Publication statusPublished - 2011

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Potential energy surfaces
Electronic structure
Hydrocarbons
Conformations
Cycloparaffins
Cyclization
Boats
Chain length
Reaction rates
Density functional theory

Keywords

  • ireland-claisen rearrangement
  • catalyzed olefin metathesis
  • ruthenium carbene complexes
  • dynamic NMR-spectroscopy
  • enantioselective synthesis
  • conformational-Analysis
  • computational methods
  • grubbs-hoveyda
  • RCM Reactions
  • force-field

Cite this

Hillier, I.H. ; Pandian, S. ; Percy, Jonathan ; Vincent, M.A. / Mapping the potential energy surfaces for ring-closing metathesis reactions of prototypical dienes by electronic structure calculations. In: Dalton Transactions. 2011 ; Vol. 40, No. 5. pp. 1061-1072.
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Mapping the potential energy surfaces for ring-closing metathesis reactions of prototypical dienes by electronic structure calculations. / Hillier, I.H.; Pandian, S.; Percy, Jonathan; Vincent, M.A.

In: Dalton Transactions, Vol. 40, No. 5, 2011, p. 1061-1072.

Research output: Contribution to journalArticle

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