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PhD Thesis, Université Paris VI
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F. Ferri, PhD Thesis, Université Paris VI, 1995, p. 63.
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33846250225
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2] see;
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2] see;
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Widenhoefer, R.A.1
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25
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33846205416
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A basicity scale in aqueous solution is given in:, Handbook of Chemistry and Physics, 52nd ed. (Ed.: R. C. Weast), The Chemical Rubber Co., Ohio, 1971-1972, p. D-177.
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A basicity scale in aqueous solution is given in:, Handbook of Chemistry and Physics, 52nd ed. (Ed.: R. C. Weast), The Chemical Rubber Co., Ohio, 1971-1972, p. D-177.
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26
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0037184431
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29
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33846236722
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It is reported that [Pd0(L)n] complexes may react with amines R2NH in oxidative addition leading to palladium(II) complexes [R2N-Pd-HLn′, L, PCy3, references [13b,c, When increasing amounts of morpholine or piperidine were added to [Pd0(PPh3)4, its oxidation peak did not disappear but was slightly shifted to more positive potentials. It became broader while the oxidation peak current increased. This indicates that the new complex(es) formed in solution were still palladium(0) complexes involved in equilibrium with the amine. Work is in progress to characterize such species better. Consequently, no oxidative addition of the amine with the Pd0 complex occurred during the timescale investigated here (10 min between each addition of amine, which is much longer than the time required for the oxidative addition (Figure 4 left, b)T. Yamamoto, K. Sano, A. Yamamoto, Chem. Lett
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0 complex occurred during the timescale investigated here (10 min between each addition of amine), which is much longer than the time required for the oxidative addition (Figure 4 left): b)T. Yamamoto, K. Sano, A. Yamamoto, Chem. Lett. 1982, 907-910;
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22244439169
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31
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33846220932
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In the absence of excess PPh3, the concentration of PPh3 varies from C0 to 3 C0 during the course of the oxidative addition due to its continuous release in the three equilibria (K1, K, and K2, Consequently, the variation of the concentration of L should have been considered in the integration of the kinetics law with [L, 3-2x)C0. Due to the complexity of the kinetics law, a constant value of [L] was con sidered for the integration of the kinetics law, equal to its average value of 2 C0 C0=2 mm
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0=2 mm).
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32
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33846248603
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From the expression for kapp given in Equation (11, we should observe a limit value at high R2NH concentrations (K 2[R2NH, L] > [L]/K1, with kapp, k4, that is, when the equilibrium between [Pd0(L) 2] and [Pd0(L)(amine, is totally shifted to the formation of [Pd0(L)(amine, which would then be the unique reactive complex. However, the reactions went too fast at high piperidine concentrations for example, t1/2=3.5s for [piperidine, 150 mM, preventing accurate data at 20 °C being obtained
-
1/2=3.5s for [piperidine] = 150 mM), preventing accurate data at 20 °C being obtained.
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34
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33846242397
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Carbopalladation of alkynes followed by trapping with nucleophilic reagents: S. Cacchi, G. Fabrizi, in the Handbook of Organopalladium Chemistry for Organic Synthesis, 1 (Ed.: E.-i. Negishi), Wiley-Interscience, New York. 2002, pp. 1335-1367;
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b) "Carbopalladation of alkynes followed by trapping with nucleophilic reagents": S. Cacchi, G. Fabrizi, in the Handbook of Organopalladium Chemistry for Organic Synthesis, Vol. 1 (Ed.: E.-i. Negishi), Wiley-Interscience, New York. 2002, pp. 1335-1367;
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35
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9944256068
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36
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33846193082
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II center occurs when they are used at the same concentration.
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II center occurs when they are used at the same concentration.
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37
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0842349083
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0 alkynes, see: a C. Amatore, S. Bensalem, S. Ghalem, A. Jutand, Y. Medjour, Eur. J. Org. Chem. 2004, 366-371;
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0 alkynes, see: a) C. Amatore, S. Bensalem, S. Ghalem, A. Jutand, Y. Medjour, Eur. J. Org. Chem. 2004, 366-371;
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25144513411
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b) M. Ahlquist, G. Fabrizi, S. Cacchi, P.-O. Norrby, Chem. Commun. 2005, 4196-4198.
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Ahlquist, M.1
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Norrby, P.-O.4
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39
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33846248216
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In the catalytic reactions, the concentrations of the piperidine and morpholine were 9.22 and 10.45 M respectively
-
In the catalytic reactions, the concentrations of the piperidine and morpholine were 9.22 and 10.45 M respectively.
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