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Heterodentate phosphines containing anionic organophosphorus groups remain virtually unexplored ligands in the coordination chemistry of coinage metals. A hybrid phosphine–phosphine oxide (o-Ph2PC6H4)2P(O)H (HP³O) readily forms the disilver complex [Ag2(P³O)2] (1) upon deprotonation of the (O)P–H fragment. Due to the electron-rich nature, the anion...