Monoligated Palladium Species as Catalysts in Cross‐Coupling Reactions

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The existence of 14‐electron T‐shaped palladium complexes as intermediates in cross‐coupling reactions has been previously questioned (see reference [70]). It was initially believed that such species would be too unstable to be detected or isolated under cross‐coupling reaction conditions. In several of the T‐shaped structures recently reported by Hartwig and co‐workers there is a stabilizing agostic interaction; however in the more recent examples such an interaction is not observed which indicates that that 14‐electron T‐shaped palladium(II) complexes can indeed be isolated.

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Amatore Jutand et al. have proposed that similar species are the active catalysts for cross‐coupling and Heck reactions when using different palladium sources/PPh3mixtures as the catalyst system. See references [9] and [71] for details.

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