Activation of white phosphorus with Ga(DDP) (DDP = 2-diiso- propylphenylamino-4-diiso-propylphenylimino-2-pentene) afforded [(DDP)Ga(P 4)] (1) by insertion of the Ga(I) center at one of the six P-P bonded edges of the P4 tetrahedron. Further reaction of 1 with three equivalents of Mo(CO)6 results in the formation of [(DDP)Ga(η2:1:1-P4){Mo(CO)5}2] 2toluene (2). Compounds 1 and 2 are characterized by 1H, 13C, and 31P NMR spectroscopy, elemental analysis, and single crystal X-ray structural analysis. The solid-state structure of molecule 1 reveals the first example of a structurally characterized GaP4 core stabilized by a β-diketiminate ligand. Compound 2 represents a rare type of coordination mode of a gallium supported P4 butterfly structure. © 2010 American Chemical Society.