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The binuclear complex [Ag2(μ-Ph2PNHPPh2)3](ClO4)2@CH2C12@CH3OH (Ph2PNHPPh2 = bis(diphenylphosphino)amine) was prepared from the reaction of AgClO4 with bis(diphenylphosphino)amine in equimolar ratio through self-assembly. The coordination cation affords a