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For significant examples of kinetic studies using reaction calorimetry, see: a
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For significant examples of kinetic studies using reaction calorimetry, see: (a) Mathew, J. S.; Klussmann, M.; Iwamura, H.; Valera, F.; Futran, A.; Emmanuelsson, E. A. C.; Blackmond, D. G. J. Org. Chem. 2006, 71, 4711-4722.
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61349109951
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(s)/mL).
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(s)/mL).
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29
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61349193055
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In the absence of Zn powder, the reaction stalled at low conversion as observed in refs 8 and 10a. We believe that the zinc dust should play a role to maintain palladium(0) complexes, avoiding inhibition processes of the catalyst system
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In the absence of Zn powder, the reaction stalled at low conversion as observed in refs 8 and 10a. We believe that the zinc dust should play a role to maintain palladium(0) complexes, avoiding inhibition processes of the catalyst system.
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30
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61349101693
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Reproducibility of the reaction heat flow profile versus time has been checked, and the heat of reaction was in average 26.8 (±1.5) kcal/mol
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Reproducibility of the reaction heat flow profile versus time has been checked, and the heat of reaction was in average 26.8 (±1.5) kcal/mol.
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31
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33645387715
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A significant induction period could be attributed to the slow activation of the catalytic precursors. A solution of Pd2(dba) 3/dppf/Zn was stirred for 20 min at rt before addition of Zn(CN) 2 and the reaction solution was equilibrated at 95°C for 45 min; no significant difference in the heat flow profile was observed with longer equilibration time 1 h, For palladium complexes activation, see: Shekhar, S, Ryberg, P, Hartwig, J. F, Mathew, J. S, Blackmond, D. G, Stricter, E. R, Buchwald, S. J. Am. Chem. Soc. 2006, 128, 3584-3591
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2 and the reaction solution was equilibrated at 95°C for 45 min; no significant difference in the heat flow profile was observed with longer equilibration time (1 h). For palladium complexes activation, see: Shekhar, S.; Ryberg, P.; Hartwig, J. F.; Mathew, J. S.; Blackmond, D. G.; Stricter, E. R.; Buchwald, S. J. Am. Chem. Soc. 2006, 128, 3584-3591.
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61349121261
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The order observed at high palladium concentration would support the presence of an inactive palladium dimer. The authors would like to acknowledge one of the referees for their comments and suggestions on the interpretation of the catalyst order
-
The order observed at high palladium concentration would support the presence of an inactive palladium dimer. The authors would like to acknowledge one of the referees for their comments and suggestions on the interpretation of the catalyst order.
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33
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61349184266
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Another possible role of zinc bromide, mentioned by one of the referees, is that it could presumably act as Lewis acid, facilitating halide abstraction from an oxidative addition intermediate
-
Another possible role of zinc bromide, mentioned by one of the referees, is that it could presumably act as Lewis acid, facilitating halide abstraction from an oxidative addition intermediate.
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34
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61349136152
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-] = 0.007 M).
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-] = 0.007 M).
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0030743672
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