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note
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For computational studies performed on this system, see refs 7b, 8g, 8h, and 8j.
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For other mechanistic investigations on Pd-catalyzed aerobic alcohol oxidations, see: (a) Steinhoff, B. A.; Fix, S. R.; Stahl, S. S. J. Am. Chem. Soc. 2002, 124, 766-767.
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44
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20444437331
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note
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PhenS = bathophenanthroline disulfonate, see ref 3e.
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45
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20444448997
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note
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IiPr = 1,3-Bis(2,6-diisopropylphenyl)-2,3-dihydro-1H-imidazole, see ref 3h.
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46
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20444489308
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note
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Upon discovering this dependence on oxidation rate on [TEA], the alcohol dependence was measured at high [TEA] (Pd:TEA = 1:20) and saturation kinetics were observed as well.
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47
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20444491697
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note
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One possibility that cannot be ruled out in the current study is direct transfer of the hydride from the palladium alkoxide to the acetate ligand.
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49
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0345491105
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Jaguar 4.0; Schrödinger, Inc.: Portland, OR, 1991-2000.
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Jaguar 4.0
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55
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20444435211
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note
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Solvent effects were in general quite small, on the level of 2-4 kcal/mol for the Pd/TEA system and somewhat larger for the Pd/pyridine system.
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57
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20444500259
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note
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The use of the effective potential LanL2DZ basis set for thermochemical analysis, namely, for acquiring thermodynamic functions and Gibbs free energy, has regularly been found to result in a level of accuracy comparable to that of superior basis sets to a small fraction of computational costs.
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58
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0001532741
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The pyridine has higher average Hartree-Fock local ionisation energy than the TEA ligand by almost 30 kcal/mol. Therefore Pd-TEA complexes with already electron-deficient Pd(II) should be more active than Pd-pyridine complexes in breaking of the C-H bond due to the more labile electronic density on the TEA ligand. For the computation of the average Hartree-Fock local ionization energy see: Brink, T. J. Phys. Chem. A 1997, 101, 3408-3415.
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