WestCHEM/Department of Pure and Applied Chemistry, University of Strathclyde, Thomas Graham Building, 295 Cathedral Street, Glasgow, G1 1XL, UK.
Chemistry. 2011 Nov 11;17(46):13087-94. doi: 10.1002/chem.201101662. Epub 2011 Oct 4.
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.
已评估了一系列简单环烯烃的热力学有效摩尔浓度，这些烯烃是通过与 Grubbs 第二代前催化剂反应从α,ω-二烯合成的。通过一系列小规模的复分解反应测量了有效摩尔浓度，并且与从转子数量和产物环应变得出的经验预测吻合良好。探索了使用电子结构计算（在 M06-L/6-311G**理论水平）来预测闭环复分解中的热力学有效摩尔浓度。然而，发现有必要对 DFT 衍生的自由能进行修正，以考虑溶剂化的熵效应。
