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Anionic Palladium(0) and Palladium(II) Ate Complexes
Author(s) -
Kolter Marlene,
Böck Katharina,
Karaghiosoff Konstantin,
Koszinowski Konrad
Publication year - 2017
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201707362
Subject(s) - palladium , iodide , chemistry , phosphine , aryl , trifluoromethyl , electrospray ionization , catalysis , heck reaction , medicinal chemistry , inorganic chemistry , ion , organic chemistry , alkyl
Palladium ate complexes are frequently invoked as important intermediates in Heck and cross‐coupling reactions, but so far have largely eluded characterization at the molecular level. Here, we use electrospray‐ionization mass spectrometry, electrical conductivity measurements, and NMR spectroscopy to show that the electron‐poor catalyst [L 3 Pd] (L=tris[3,5‐bis(trifluoromethyl)phenyl]phosphine) readily reacts with Br − ions to afford the anionic, zero‐valent ate complex [L 3 PdBr] − . In contrast, more‐electron‐rich Pd catalysts display lower tendencies toward the formation of ate complexes. Combining [L 3 Pd] with LiI and an aryl iodide substrate (ArI) results in the observation of the Pd II ate complex [L 2 Pd(Ar)I 2 ] − .