Journal of Physical Chemistry p. 383 - 389 (1986)
Update date:2022-08-02
Topics:
Arnett, Edward M.
Molter, Kent
Rate data are presented for the heterolysis of carbon-carbon bonds and their formation through coordination of resonance-stabilized carbocations and carbanions in acetonitrile solution at 25 deg C.These rates were determined by NMR line broadening and by the T jump technique (in a solution containing 0.48 M supporting electrolyte).Preliminary results are given for a "master equation" to predict some heterolysis energies in solution as a complement to Benson's method for homolysis energies.The results provide for the first time an opportunity to compare the effects of structure variation on the kinetic and thermodynamic properties for such an ostensibly simple reaction in solution.All evidence so far accumulated indicates that these reactions are dominated by ion-solvation factors so that they have little bearing on the gas-phase heterolysis energies.Ionic strength effects and substituent variation suggest that charge development is about half developed at the transition state, but we argue that this cannot be translated simply into pictures of transition-state structure.The results provide a flagrant reversal of the frequently invoked "reactivity selectivity principle" since the most reactive cation is also most selective.On the basis of these results and many others which have appeared recently it may be appropriate to discard the reactivity selectivity principle as a useful principle for either prediction or interpretation.
View MoreWuhan Hanye Chemical New Material Co.,Ltd
Contact:+86-27-85308141
Address:LiuDian, Panlongcheng Economic Development Zone, HuangPi district, Wuhan, Hubei 430311 P.R.China
Shanghai Mintchem Development ., Ltd
Contact:0086 21 5190 8570
Address:R602,4#,89Nong, Mudan Road Pudong Shanghai China
JiangXi Keyuan Biopharma Co., LTD.
Contact:+86-563-6833666
Address:Guangde Fine Chemical Zone, Anhui Province, China
Shijiazhuang Haotian Chemical Co., Ltd.
Contact:86-311-85044374
Address:293 Donggang Road
MTT Pharma & Bio-technology Co.,Ltd
Contact:+86-21-58407925
Address:Room2019, Building C, Tomson Center, No.158, Zhang Yang Road, Shanghai, China
Doi:10.1016/j.tet.2006.09.074
(2006)Doi:10.1016/S0040-4039(00)86749-0
(1982)Doi:10.1021/ja063132m
(2006)Doi:10.1016/j.bmc.2006.10.017
(2007)Doi:10.1016/j.poly.2006.06.015
(2006)Doi:10.1016/S0040-4020(01)98455-8
(1964)