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33645467551
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2 (recrystallized from toluene) in DMSO results in rapid disproportionation. In contrast, if hydrogen peroxide is added to a suspension of palladium black obtained from a completed catalytic reaction, disproportionation is slow. These observations suggest that the Pd-catalyzed disproportionation mechanism may proceed via a Pd(II)TPd(IV) cycle.
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49
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0003059597
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Rylander, P. N., Greenfield, H., Eds.; Academic Press: New York
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Such a rate law has been observed for the aerobic oxidation of a well-defined Pd(0) complex, for example: Stahl, S. S.; Thorman, J. L.; Nelson, R. C.; Kozee, M. A. J. Am. Chem. Soc. 2001, 123, 7188-7189.
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33645462068
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2] dependence is therefore explained by invoking a higher-order (>1) dependence of the decomposition rate on [Pd].
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33645470379
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2/pyridine-catalyzed reaction also reveal saturation dependence on [alcohol] (cf. Figure 3B); however, a first-order approximation for the [alcohol] dependence led to a very good exponential fit of the reaction timecourse.
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33645473695
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hi).
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33645473985
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It might be expected that a different set of rate equations would apply to reactions that exhibit mass-transfer-limitation effects because the rate is formally not dependent on the [alcohol] under these conditions. However, only the initial rate is limited by mass-transfer effects. Analysis of the timecourse data reveals that the reaction rate quickly falls below the mass-transfer limit (i.e., within the first few minutes), and >95% of the data is acquired under conditions that exhibit the typical [alcohol] dependence.
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This observation underlies our current interest in the effects of the catalyst coordination environment on the rates of palladium(0) oxygenation. See ref 14 and the following: Konnick, M. M.; Guzei. I. A.; Stahl, S. S. J. Am. Chem. Soc. 2004, 126, 10212-10213.
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Konnick, M.M.1
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Safety is also a critical consideration in these reactions. In many cases, conditions that employ organic solvents with I atm of oxygen pressure fall within the explosive limits. Specific safety assessments generally must be conducted on a case-by-case basis.
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