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The PdII-OOH complex 2 has been prepared independently via protonolysis of (IMes)2PdIIη2-O 2, See ref 6b and Supporting Information for details
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2). See ref 6b and Supporting Information for details.
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56
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36248985268
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See Supporting Information for further details. Analogous ligand oxidation has been observed previously for a cobalt-hydroperoxide complex (see ref 12m, In addition, ligand decomposition in Pd-catalyzed aerobic oxidation of alcohols has been proposed to proceed via the reaction of an (unobserved) hydroperoxide intermediate with a ligand benzylic methyl group: Conley, N. R, Labios, L. A, Pearson, D. M, McCrory, C. C. L, Waymouth, R. M Organometallics 2007, 26, 5447-5453
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See Supporting Information for further details. Analogous ligand oxidation has been observed previously for a cobalt-hydroperoxide complex (see ref 12m). In addition, ligand decomposition in Pd-catalyzed aerobic oxidation of alcohols has been proposed to proceed via the reaction of an (unobserved) hydroperoxide intermediate with a ligand benzylic methyl group: Conley, N. R.; Labios, L. A.; Pearson, D. M.; McCrory, C. C. L.; Waymouth, R. M Organometallics 2007, 26, 5447-5453.
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In our preliminary communication of the reaction between 1 and O2 (ref 10, we reported clean, first-order kinetics for the oxygenation of 1 in the absence of additives. In subsequent studies, however, we determined that our original Pd-hydride samples contained trace amounts of BzOH that slightly increase the rate of the oxygenation reaction and result in clean, exponential kinetics. The BzOH originates from the synthesis of 1 and is not readily detected by NMR spectroscopy because it equilibrates with the BzO- ligand coordinated to Pd see Discussion later in this paper, In order to avoid this complication, subsequent syntheses of 1 were performed with a slight deficiency of BzOH relative to the Pd0 precursor
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0 precursor.
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4OBz and BzOH; see previous section for details) or at low benzoate concentrations; in these cases, initial rate data were used.
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4OBz and BzOH; see previous section for details) or at low benzoate concentrations; in these cases, initial rate data were used.
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2 solubility and issues related to mass-transfer into solution, see: (a) Steinhoff, B. A.; Guzei, I. A.; Stahl, S. S J. Am. Chem. Soc. 2004, 126, 11268-11278.
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2 solubility and issues related to mass-transfer into solution, see: (a) Steinhoff, B. A.; Guzei, I. A.; Stahl, S. S J. Am. Chem. Soc. 2004, 126, 11268-11278.
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2). These empirical observations suggest that both radical and non-radical pathways might be involved.
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2). These empirical observations suggest that both radical and non-radical pathways might be involved.
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2 and the Pd-hydride complex.
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2 and the Pd-hydride complex.
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A concerted reductive-elimination pathway has been identified by DFT calculations (see ref 16 and the discussion below), and the computations support a small isotope effect for this pathway. The calculated kinetic isotope effect for reductive elimination of acetic acid from a closely related model complex is 1.6. Popp, B. V.; Stahl, S. S., unpublished results.
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A concerted reductive-elimination pathway has been identified by DFT calculations (see ref 16 and the discussion below), and the computations support a small isotope effect for this pathway. The calculated kinetic isotope effect for reductive elimination of acetic acid from a closely related model complex is 1.6. Popp, B. V.; Stahl, S. S., unpublished results.
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2 is lower by 6.4 kcal/mol when the hydride ligand is trans to a methyl group rather than a carboxylate ligand.
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2 is lower by 6.4 kcal/mol when the hydride ligand is trans to a methyl group rather than a carboxylate ligand.
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