title: Why is RCM favoured over dimerisation? Predicting and estimating thermodynamic effective molarities by solution experiments and electronic structure calculations.
abstract: The thermodynamic effective molarities of a series of simple cycloalkenes, synthesised from α,ω-dienes by reaction with Grubbs' second generation precatalyst, have been evaluated. Effective molarities were measured from a series of small scale metathesis reactions and agreed well with empirical predictions derived from the number of rotors and the product ring strain. The use of electronic structure calculations (at the M06-L/6-311G** level of theory) was explored for predicting thermodynamic effective molarities in ring-closing metathesis. However, it was found that it was necessary to apply a correction to DFT-derived free energies to account for the entropic effects of solvation.
authors.affiliation: WestCHEM/Department of Pure and Applied Chemistry, University of Strathclyde, Thomas Graham Building, 295 Cathedral Street, Glasgow, G1 1XL, UK.
authors.forename: David J
authors.initials: DJ
authors.lastname: Nelson
authors.forename: Ian W
authors.initials: IW
authors.lastname: Ashworth
authors.forename: Ian H
authors.initials: IH
authors.lastname: Hillier
authors.forename: Sara H
authors.initials: SH
authors.lastname: Kyne
authors.forename: Shanthi
authors.initials: S
authors.lastname: Pandian
authors.forename: John A
authors.initials: JA
authors.lastname: Parkinson
authors.forename: Jonathan M
authors.initials: JM
authors.lastname: Percy
authors.forename: Giuseppe
authors.initials: G
authors.lastname: Rinaudo
authors.forename: Mark A
authors.initials: MA
authors.lastname: Vincent
mesh_terms: D000465:Algorithms; D002384:Catalysis; D003500:Cyclization; D003516:Cycloparaffins / Q000138:chemical synthesis / Q000737:chemistry*; D019281:Dimerization; D015394:Molecular Structure; D013816:Thermodynamics
chemical_list: D003516:Cycloparaffins