Table 1 Comparison of the rates of isolated elementary steps with the catalytic reaction between 1aand 2a.

From: Elucidating the reaction mechanism of a palladium-palladium dual catalytic process through kinetic studies of proposed elementary steps

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Entry

Reaction

Rate (μmol/Ls)

1

OA of 1a into 7a

instant

2

TM of 7a’ and 6a

1.59a

3

Formation of 6a from 5a

7.40

4

Catalytic reaction of 1a and 2a

7.26

  1. In all cases the concentration of palladium precatalyst or reagent(s) was the 0.01 M for the compared reactions, i.e., Pd(PPh3)2I2 for the catalytic reaction, Pd(PPh3)4 for oxidative addition into 7a, and 6a and 7a’ for transmetallation reaction. The reactions were performed in dichloromethane or CDCl3 at RT (296 K) in the presence of pyrrolidine, apart from TM reaction. The rates of studied stoichiometric and catalytic reactions are similar in CH2Cl2 and CHCl3 (CDCl3). aThe actual rate is most likely higher than the observed rate due to decomposition of 7a’, without the decomposition of 7a’, the rate would probably be > 8 μmol/Ls. For more details see the Supplementary Note 1. Pyr = pyrrolidine; Ar = 4-CH3-C6H4-; R = Ph.
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