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By simply mixing with phosphine or carbene ligands, they are in situ converted into well\u2010defined monoligated complexes. Their catalytic performance was benchmarked against state\u2010of\u2010the\u2010art systems in challenging Buchwald\u2013Hartwig, Heck, Suzuki and Negishi couplings, and ketone arylations. Their use enabled record\u2010setting activities, beyond those achievable by optimization of the ligand alone. 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