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[10] the precatalysts are extensively washed and extracted in hot solvents to insure that physisorbed species are removed from the materials before they are used in Heck reactions.
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We note that the temperatures and solvents used in the acid-catalyzed dimerization and in the Heck reaction are different. However, we have confirmed that PVPy is largely insoluble in DMF at reaction temperature using the following test. PVPy was heated in DMF at the reaction temperature for 30 min. The PVPy was subsequently removed by filtration and the remaining liquid was used as the solvent for a Heck reaction with added 1. The kinetics of this reaction were unchanged compared to standard conditions using 1 as the precatalyst. Thus, there was no appreciable soluble PVPy in solution.
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76
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14644406394
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note
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With limited characterizations on material 6 (characterized by FT-Raman). we are not able to confirm that only the SCS-Pd pincer (with a Pd-C bond) was formed, and it is possible that small amount of coordination complex that does not have a Pd-C bond is formed during palladation.
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78
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[14]
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[14]
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84
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14644433260
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note
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TEM images of the precursor complex 1 and the reaction solution were taken in an attempt to document potential nanoparticle formation (Pd black formation was documented visually in the reaction solution). However, the data proved to be inconclusive.
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85
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3142760135
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[9a,10] imply that other Pd(II)-SCS complexes that are claimed to be recyclable and recoverable likely also decompose: D. P. Curran, K. Fischer, G. Moura-Letts, Synlett 2004, 1379.
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