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The reactions examined here are net hydrogen atom transfers. Other work in progress in our laboratories indicates that they follow a concerted HAT mechanism as well, but this is independent of the thermochemical results here. See refs 28, 31.
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The reactions examined here are net hydrogen atom transfers. Other work in progress in our laboratories indicates that they follow a concerted HAT mechanism as well, but this is independent of the thermochemical results here. See refs 28, 31.
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-
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84869565864
-
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soln is still being debated in the literature revolves around the magnitude of solvation energies in different solvents and how best to interconvert between them. These effects are potentially magnified when dealing with transition metal complexes because of the increased polarity changes between oxidations states.
-
soln is still being debated in the literature revolves around the magnitude of solvation energies in different solvents and how best to interconvert between them. These effects are potentially magnified when dealing with transition metal complexes because of the increased polarity changes between oxidations states.
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0000411496
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It should be noted that the conversion between standard states in refs 45b and 45c do not correctly account for the unit mol fraction standard state in solution or the conversion between 1 atm and 1 M standard states in the gas phase
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0022093150
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Using ΔH°solv[H•]s ≅ Delta;H°solv[H2]s= 1.56, 1.38, and 1.81 kcal mol-1 for MeCN, toluene, and ClCH2CH2Cl, respectively. Delta;H°solv[H•]MeCN ≅ Delta;H°solv[H2]MeCN= 5.12 kcal mol-1: Brunner, E. J. Chem. Eng. Data 1985, 30, 269-273
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-
-
84869576959
-
-
This model is parameterized into the acidity (αH 2) and the basicity (βH 2) of the hydrogen bond donor and acceptor
-
2) of the hydrogen bond donor and acceptor.
-
-
-
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134
-
-
84869559294
-
-
s-
-
s-
-
-
-
-
135
-
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84869587095
-
-
s.
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s).
-
-
-
-
136
-
-
84869565859
-
-
C6H6 ≅-
-
C6H6 ≅-
-
-
-
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137
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0037414534
-
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2,solvent-1.094. From Litwinienko, G.; Ingold, K. U. J. Org. Chem. 2003, 68, 3433-3438, and ref 48b:
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2,solvent-1.094. From Litwinienko, G.; Ingold, K. U. J. Org. Chem. 2003, 68, 3433-3438, and ref 48b:
-
-
-
-
138
-
-
84869576955
-
-
2(benzene) = 0.14.
-
2(benzene) = 0.14.
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139
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84961984968
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84869587093
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-1). Entropies of formation from refs 52b- e.
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See also ftp://ftp.technion.ac.il/pub/supported/aetdd/thermodynamics
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Note that spin-crossover entropies are substantially larger than expected solely from the electronic multiplicities. For example, AS° elec is- 5.4 cal mol-1 K-1 for high-spin 5T2g Fen low-spin ⇄A1g FeII, much less than the measured ΔS°SCO, 21 cal mol-1 K-1 for Fen(H 2bip).31
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31
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194
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84869576947
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59 complexes of Co and Ru.
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59 complexes of Co and Ru.
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195
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84869559287
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67
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67
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196
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197
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84869587086
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62 because other effects can contribute.67
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62 because other effects can contribute.67
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198
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84869565852
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-1 in MeCN,
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-1 in MeCN,
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199
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84869559289
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3+/2+ = 27.9
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3+/2+ = 27.9
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200
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84869576939
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60a
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60a
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201
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0028925951
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