Salt Effects and Ion Pairs in Solvolysis and Related Reactions. XXI.1Acetolysis, Bromide Exchange and the Special Salt Effect2

1961 ◽  
Vol 83 (24) ◽  
pp. 4986-4989 ◽  
Author(s):  
S. Winstein ◽  
Paul E. Klinedinst ◽  
E. Clippinger
Keyword(s):  
Ion Pairs ◽  
Salt Effects

Picosecond dynamics of contact ion pairs: solvent and salt effects

1991 ◽  
Vol 95 (11) ◽  
pp. 4177-4179 ◽  
Author(s):  
T. Yabe ◽  
S. Sankararaman ◽  
Jay K. Kochi
Keyword(s):  
Ion Pairs ◽  
Salt Effects ◽  
Contact Ion Pairs

Kinetic evidence for the importance of solvent-separated ion pairs during the solvolyses of adamantylideneadamantyl derivatives

2004 ◽  
Vol 82 (9) ◽  
pp. 1336-1340
Author(s):  
Xicai Huang ◽  
Andrew J Bennet
Keyword(s):  
Ionic Strength ◽  
Transition State ◽  
Isotope Effect ◽  
Kinetic Isotope Effect ◽  
Isotope Effects ◽  
Ion Pairs ◽  
Kinetic Isotope Effects ◽  
Ion Pair ◽  
Salt Effects ◽  
Kinetic Isotope

The aqueous ethanolysis reactions of adamantylideneadamantyl tosylate, -bromide, and -iodide (1-OTs, 1-Br and 1-I) were monitored as a function of ionic strength. Special salt effects are observed during the solvolyses of both homoallylic halides, but not in the case of the tosylate 1-OTs. The measured α-secondary deuterium kinetic isotope effects for the solvolysis of 1-Br in 80:20 and 60:40 v/v ethanol–water mixtures at 25 °C are 1.110 ± 0.018 and 1.146 ± 0.009, respectively. The above results are consistent with the homoallylic halides reacting via a virtual transition state in which both formation and dissociation of a solvent-separated ion pair are partially rate-determining. While the corresponding transition state for adamantylideneadamantyl tosylate involves formation of the solvent-separated ion pair.Key words: salt effects, kinetic isotope effect, internal return, solvolysis, ion pairs.

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