2015
DOI: 10.1002/chem.201406408
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Catalyst Activation, Deactivation, and Degradation in Palladium‐Mediated Negishi Cross‐Coupling Reactions

Abstract: Pd-mediated Negishi cross-coupling reactions were studied by a combination of kinetic measurements, electrospray-ionization (ESI) mass spectrometry, (31)P NMR and UV/Vis spectroscopy. The kinetic measurements point to a rate-determining oxidative addition. Surprisingly, this step seems to involve not only the Pd catalyst and the aryl halide substrate, but also the organozinc reagent. In this context, the ESI-mass spectrometric observation of heterobimetallic Pd-Zn complexes [L2 PdZnR](+) (L=S-PHOS, R=Bu, Ph, B… Show more

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Cited by 54 publications
(49 citation statements)
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“…[1][2][3][4][5] The introduction of electrospray ionization (ESI) allowed direct probing of reaction mixtures and ESI-MS was established as a method for "fishing out" reaction intermediates. 6,7 A big advantage of using ESI-MS is its sensitivity. Reactive intermediates that are often present at very low concentrations can be detected, isolated in the gas phase and can have their reactivity probed.…”
Section: Introductionmentioning
confidence: 99%
“…[1][2][3][4][5] The introduction of electrospray ionization (ESI) allowed direct probing of reaction mixtures and ESI-MS was established as a method for "fishing out" reaction intermediates. 6,7 A big advantage of using ESI-MS is its sensitivity. Reactive intermediates that are often present at very low concentrations can be detected, isolated in the gas phase and can have their reactivity probed.…”
Section: Introductionmentioning
confidence: 99%
“…In general, organozinc reagents are less reactive than the corresponding Grignard reagents. [7] Even more surprising is the observation of the stable Pd IV species[ PdBn 5 ] À under the present conditions. [9] However,t hese reactions occurred under conditions differentf rom the present ones.…”
Section: Discussion Efficiencyoft He Transmetallationmentioning
confidence: 77%
“…Thep resence of Pd 0 -Zn complexes in Negishi reactions was recently reported in the literature, [15] but their photochemical behavior remained unknown. Thep resence of Pd 0 -Zn complexes in Negishi reactions was recently reported in the literature, [15] but their photochemical behavior remained unknown.…”
Section: Angewandte Chemiementioning
confidence: 96%