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0344676046
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note
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Reactions of 3 and 5 are more sensitive to the presence of the metal ion than the corresponding reactions of 4 and 6 because binding to the barium ion transforms an electron-donating (rate-retarding) carboxylate into an electron-withdrawing (rate-enhancing) carboxylatemetal ion pair.
-
-
-
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29
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0345538273
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-
note
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The close similarity of the two values would indicate that the higher affinity for the monometallic complex of the more basic AcO ion is substantially counterbalanced by the statistical factor 2 which operates in the binding of the less basic 3 to the bimetallic complex. The fact that the ligand is not exactly the same in the two cases is presumably unimportant.
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30
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77956770660
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inter refers to the intermolecular model reaction. For a discussion of structure effects on the EM value see: a) A. J. Kirby, Adv. Phys. Org. Chem. 1980, 17, 183-278; b) L. Mandolini, Adv. Phys. Org. Chem. 1986, 22, 1-111.
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