Mapping the potential energy surfaces for ring-closing metathesis reactions of prototypical dienes by electronic structure calculations
Hillier, I.H. and Pandian, S. and Percy, Jonathan and Vincent, M.A. (2011) Mapping the potential energy surfaces for ring-closing metathesis reactions of prototypical dienes by electronic structure calculations. Dalton Transactions, 40 (5). pp. 1061-1072. ISSN 1472-7773 (https://doi.org/10.1039/c0dt01314e)
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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
ORCID iDs
Hillier, I.H., Pandian, S., Percy, Jonathan ORCID: https://orcid.org/0000-0001-8636-2704 and Vincent, M.A.;-
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Item type: Article ID code: 30245 Dates: DateEvent2011PublishedSubjects: Science > Chemistry Department: Faculty of Science > Pure and Applied Chemistry Depositing user: Pure Administrator Date deposited: 31 Mar 2011 13:19 Last modified: 11 Nov 2024 09:42 URI: https://strathprints.strath.ac.uk/id/eprint/30245