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Interestingly, whereas best results were achieved with DMF when electronically activated or non-activated aryl bromides were applied, NMP was the solvent of choice when electronically deactivated and sterically hindered or heterocyclic aryl bromides were coupled with alkenes Tetrabutylammonium bromide is known to stabilize such nanoparticles but has a retarding effect in catalyses when molecular mechanisms are operative. See for instance
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Notably, the cross-coupling product of 5,5′-dibromo-2,2′- bithiophene and 4-acryloylmorpholine-4,4′-{2,2′-bithiene-5,5′- diylbis[(1E)-3-oxoprop-1-ene-1,3-diyl]}dimorpholine-is a red, THF soluble solid, which forms a yellow precipitate in the presence of potassium bromide and, hence, under reaction conditions.
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To be more precise: whereas (in contrast to 4) excellent, but comparable levels of activity were observed for dichloro-bis(aminophosphine) complexes of palladium at 140 °C when electronically activated and non-activated substrates were coupled, the far highest level of activity was observed for dichloro-bis(1-(dicyclohexylphosphinyl)piperidine)palladium (3) when electronically deactivated or sterically hindered and, hence, difficult-to-couple aryl bromides were applied.
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PVPy is a palladium trap, which can effectively inhibit catalysis when nanoparticles are the catalytically active form of a catalyst. Nevertheless, it should be mentioned that Pd nanoparticles immobilized on PVPy spheres also have been applied as a catalyst in Heck reactions. 28 Therefore, this test is not definitive and does neither conclusively prove nor rule out either catalysis by the surface of Pd nanoparticles or molecular Pd(0) species (for itself) but can strongly support the conclusions drawn from other tests performed. For details see
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