Why is RCM favoured over dimerisation? Predicting and estimating thermodynamic effective molarities by solution experiments and electronic structure calculations

Nelson, David J and Ashworth, Ian W. and Hillier, Ian H. and Kyne, Sara H and Pandian, Shanthi and Parkinson, John A and Percy, Jonathan M and Rinaudo, Giuseppe and Vincent, Mark A. (2011) Why is RCM favoured over dimerisation? Predicting and estimating thermodynamic effective molarities by solution experiments and electronic structure calculations. Chemistry - A European Journal, 17 (46). pp. 13087-13094. ISSN 1521-3765 (http://dx.doi.org/10.1002/chem.201101662)

Full text not available in this repository.Request a copy

Abstract

The thermodynamic effective molarities of a series of simple cycloalkenes, synthesised from ,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.

  • Item type:Article
    ID code:35397
    Dates:
    Date
    Event
    11 November 2011
    Published
    Keywords:thermodynamics, homogeneous catalysis, cycloalkenes, metathesis, ring closure, Chemistry, Chemistry(all)
    Subjects:Science > Chemistry
    Department:Faculty of Science > Pure and Applied Chemistry
    Depositing user: Pure Administrator
    Date deposited:28 Oct 2011 13:08
    Last modified:08 Apr 2014 04:02
    URI:https://strathprints.strath.ac.uk/id/eprint/35397
CORE (COnnecting REpositories)