Solvent Effects on the Reactions of Stabilized Carbonium Ions with Nucleophiles

The Study of Reactive Intermediates in Condensed Phases

“…38 In such discussions there is usually the implicit (sometimes explicit) assumption that the solvent can respond instantaneously to changes in solute polarity. 39 However, as this Perspective will seek to illustrate, there are reasons to believe that these common assumptions about the effects of solvents are incomplete and, in some cases, simply wrong. On the energy front, for example, it is notable that Baldwin 40 …”

Nucleophilie‐ und Elektrophilieskalen als Ordnungsprinzipien polarer organischer und metallorganischer Reaktionen

“…In den Arbeitskreisen von Ritehie [20] und Kane-Maguire 1211 wur den meist Stopped-flow-Techniken (UV/VIS) eingesetzt, mit de nen auch schnellere Reaktionen untersucht werden können. Bei Carbonylkomplexen wurde auch die IR-Spektroskopie verwen det [21] .…”

Cation–anion combination reactions. 26. A review

“…quat ti on / I ] , the N A on the dimethylamino group, combinations of acidity functions 'For Parts 1 to 25, see refs. 1 to 25. are useful (12). xanthylium cation 1,3,6.8-Tetra-OCH; xanthylium cation' 3,6-Bis-OCH; xanthylium cation' 9-CH;, 3,6-bis-0CH3 xanthylium cation' 9-CH3, 1 Aryldiazonium ions react in basic aqueous solutions to form, in the first observable reactions, the syn-diazotates (2).…”

“…If the transition states were solvated as stable species, the solvation would also be expected to be intermediate between that of reactants and products. Quite specifically, the effect of changing solvent on the rate constant for such a reaction would be expected to be smaller than the effect of the equilibrium constant (1).…”