Catalysis pseudo intramolecular

In another interesting example of pseudo intramolecular catalysis, the halftime for the methanolysis of the calixarene monoacetate 290a with Mc4N OMe in MeOH at 25 °C is reduced from 34 weeks to 8 seconds by the addition of The reactive species is thought to be the Ba complex of the... 

First-order and second-order rate constants have different dimensions and cannot be directly compared, so the following interpretation is made. The ratio ki k,ma has the units mole per liter and is the molar concentration of reagent Y in Eq. (7-72) that would be required for the intermolecular reaction to proceed (under pseudo-first-order conditions) as fast as the intramolecular reaction. This ratio is called the effective molarity EM), thus EM = kimnJk,Ma- An example is the nucleophilic catalysis of phenyl acetate hydrolysis by tertiary amines, which has been studied as both an intermolecular and an intramolecular process. ... 

The occurrence of intramolecular metal ion catalysis is reported in the hydrolysis of adenylyl(3 -5 )adenosine (ApA) under the presence of diaquatetraazaco-balt(lll) complexes [Co(N)4(OH2)2] + (N coordinated nitrogen atom) at pH 7.0. Pseudo-first-order rate constants (ko,J for ApA hydrolysis at 50°C and 0.1 M Co " complexes are lO times larger than k.,b 50°C and [Co " complex] = 0. 

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