Abstract
AbstractThe logarithm of heterolysis rates of 4‐methoxyneophyl tosylate, Et3CBr,tert‐BuCl, andtert‐BuBr in a set of 12 to 28 hydrogen‐bond (HB) and non‐HB donor solvents are correlated to four sets of solvent parameters: (a)ET(30), (b)π*,α,β, (c)SP,SdP,SA,SB, and (d)DI,ES,α1,β1. Disjointed results are found for Et3CBr because of an insufficient diversity of solvents. For the other solvolyses, the determination coefficientsr2are good to excellent, the gas‐phase values are fairly predicted, and the contributions of various intermolecular forces to the global solvent effect agree satisfactorily within the four solvent sets. However, the most complete description of the solvent effect is given by the four‐parameter sets because their parameters refer to a single intermolecular force, whereasET(30) andπ*correspond to a fixed blend of solute/solvent interactions. For the application of theDI,ES,α1, andβ1set to correlatetert‐BuCl solvolysis,r2= .976, lgk(gas) = −18.6 (experimental −19.3), and the contributions of HB donation (α1), electrostatic forces (ES), and dispersion‐induction (DI) to the solvent effect amounts to 59%, 21%, and 14%, respectively. The dependence of rates on the solvent HB basicity is nearly zero. The inclusion of the solvent cohesive energy density parameterinto the correlation equations does not improve these correlations.
Sign-in/Register to access full text options 
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a callDisclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.
