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0 = κ(kT/h), κ accounts for the possibility that the activated complex (transition state) will give the reactants back, rather than the products. For discussion, see chapter 4 in Laidler, K. J. Chemical Kinetics.
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note
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The term "nonadiabatic" is used in this study in a generic sense to denote a reaction having rate constant with a small preexponential value, in a way similar to that adopted by Balzani. For a discussion on the use of the term in reaction kinetics see Laidler in the next reference.
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85037296031
-
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The registry numbers of 1 and 2 are 4754-92-1, and 4755-00-4, respectively. 3 is a new compound and was prepared by a similar way as described for 1 and 2 in ref 10
-
The registry numbers of 1 and 2 are 4754-92-1, and 4755-00-4, respectively. 3 is a new compound and was prepared by a similar way as described for 1 and 2 in ref 10.
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2 in data fitting, but does not change the conclusions of the study.
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Nonlinear regression was done using Mathematica V.3.0.1
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Nonlinear regression was done using Mathematica V.3.0.1.
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note
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The chemical shift of the amide proton of 1 appears at 9.42 ppm (CD2C12, 25 °C). The relatively low field value of this proton can be attributed to a presence of a weak side-on intramolecular hydrogen bond between this proton and the azomethine nitrogen.
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85037318967
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max
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70
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85037312027
-
-
note
-
2 at 30 °C appear as sharp peaks at 8.47 and 9.37 ppm in the NMR spectrum. Upon cooling, the peak at 8.47 ppm (peak width = 6.6 Hz) is gradually shifted to lower field values, and is slightly broadened, reflecting presence of two rapidly exchanging species in solution having very different environments around this amide proton. At -70°, the chemical shift of this peak is 9.56 ppm, and the peak width is 18.7 Hz. These environments are consistent with presence or absence of a strong intramolecular H-bond involving this proton. The value of the peak at 9.37 ppm is similar to the chemical shift of the anilide proton of 1 (9.42 ppm), and may therefore be attributed to a proton having a side-on intramolecual H-bond with the azomethine nitogen. The chemical shift of this proton does not change upon cooling. All these results are consistent with the proposition that the two exchanging species differ only in the rotation of one of the anilide groups. We thank Andrew Hoteling for doing the NMR measurements.
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