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.

DOI: 10.1002/chem.201101662

Cite this paper

@article{Nelson2011WhyIR, title={Why is RCM favoured over dimerisation? Predicting and estimating thermodynamic effective molarities by solution experiments and electronic structure calculations.}, author={David J Nelson and Ian W. Ashworth and Ian H. Hillier and Sara H. Kyne and Shanthi Pandian and John A. Parkinson and Jonathan M. Percy and Giuseppe Rinaudo and Mark A. Vincent}, journal={Chemistry}, year={2011}, volume={17 46}, pages={13087-94} }