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For the dehydrogenation of ethane, the thermodynamic parameters are ΔH = 32.7 kcal/mol, ΔS = 28.8 cal/(mol K) at 293.15 K, ΔG = 24.3 kcal/mol: Atkins, P.; de Paula, J. Atkins' Physical Chemistry; 7th ed.; Oxford University Press: New York, 2002.
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47949132892
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For tables and figures of these quantities, see the Supporting Information
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For tables and figures of these quantities, see the Supporting Information.
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78
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47949114250
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For the calculation of the energy of the species involved, these authors use a process where the atomization energies are calculated and implemented together with known heats of formation of the relevant atoms to obtain the heats of formation at 0 K.
-
For the calculation of the energy of the species involved, these authors use a process where the atomization energies are calculated and implemented together with known heats of formation of the relevant atoms to obtain the heats of formation at 0 K.
-
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80
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47949128811
-
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5-containing compounds were not calculated due to their expense.
-
5-containing compounds were not calculated due to their expense.
-
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81
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0000010511
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For another computational study on bond dissociation enthalpies including some amine-boranes, see: a
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3 is under debate. While a commonly used explanation is that the Lewis acidity is a trade off between σ-withdrawing and π-donating effects, this has been contested by Frenking: (b) Bessac, F; Frenking, G. Inorg. Chem. 2003, 42, 7990.
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47949123305
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This effect is less visible with the B3LYP calculations. Therefore, we repeated the calculations on the MP2/6-31G(d,p) level of theory for all compounds of the type X2NH-BH3 and H3N-BHX 2 with X, H, F, Cl, and Br and the corresponding dehydrogenated products. The results are given in the Supporting Information
-
2 with X = H, F, Cl, and Br and the corresponding dehydrogenated products. The results are given in the Supporting Information.
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We tested the possibility that HOTf may be preferentially released rather than hydrogen. We found that, thermodynamically, this is not expected
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We tested the possibility that HOTf may be preferentially released rather than hydrogen. We found that, thermodynamically, this is not expected.
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It has been suggested that B3LYP may predict less exothermic reactions for dimerizations such as the ones described: Bissett, K. M.; Gilbert, T. M. Organometallics 2004, 23, 850. However, this was shown for only one example.
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