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

Nelson, D. J. and Ashworth, I. W. and Hillier, I. H. and Kyne, S. H. and Pandian, S. and Parkinson, J. A. and Percy, J. M. and Rinaudo, G. and Vincent, M. 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 0947-6539

Full content URL: http://dx.doi.org/10.1002/chem.201101662

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Abstract

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

Keywords:Cycloalkenes, Metathesis reactions, Homogenous catalysis
Subjects:F Physical Sciences > F160 Organic Chemistry
F Physical Sciences > F161 Organometallic Chemistry
Divisions:College of Science > School of Chemistry
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ID Code:17616
Deposited On:10 Jun 2015 15:53

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