We synthesized phosphanylphosphaalkenes (biph)₂C=P-P(tBu)₂ (2), Ph₂C=P-P(NEt₂)₂ (3), and (biph)₂C=P-P(NEt₂)₂ (4). The diaminophosphanyl derivatives reversibly dimerize head-to-head and react with a ruthenium complex, leading to P-P bond activation and the formation...