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th + RT, and the Gibbs free energy is G = H - TS.
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34
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0028316720
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2), which are particularly closely related to the nonclassical intermediates calculated in this work. Six values were determined for ΔS‡. ranging from 0.7 ± 1.0 to 3.7 ± 1.1 eu: (a) Hauger, B. E.; Gusev, D.; Caulton, K. G. J. Am. Chem. Soc. 1994, 116, 208-214.
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2142820241
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H2elim. Extrapolating from the enthalpy difference in this case gives a free energy of 38.8 kcal/mol. The average of these two values. 37.4 kcal/mol, is shown in Figure 7. The basis for this estimation method is well established, particularly for related "seven-coordinate" iridium complexes (see ref 21).
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38
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2142648076
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r-BuPCP)Ir(Ph)H (ref 9).
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39
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2142646698
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25,26
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2142758917
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note
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The relative differences in the addition rates among different alkane substrates for kinetic measurements are usually much smaller than those observed in the present case. This is probably because direct measurements of addition rates necessarily involve exothermic additions, whereas in the present case the rate-determining step is endothermic. Thus, the transition state is late and, perhaps more importantly, our kinetic barriers include a thermodynamic barrier. Thermodynamic variations among additions of various hydrocarbons are often found to be of the same order of magnitude as those in the present case.
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Most of the currently available functionals (including B3LYP) underestimate intermolecular binding energies and charge-transfer effects at long range. It is possible that the B3LYP functionals differentially overestimate the energies in metal complexes with high coordination numbers and in the transition states, which lead to the formation of these complexes. See, for example: (a) Paizs, B.; Suhai, S. J. Comput. Chem. 1998, 19, 575.
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2(sol] for linear olefins at the concentrations monitored (> ca. 10 mM), but not for cyclooctene at concentrations in which the stirring rate was varied (< ca. 100 mM).
-
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57
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2142761835
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note
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I is reported to be approximately 18 kcal/mol lower in enthalpy than these final products (Table 1 of ref 13).
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