The potassium salt of a new ligand, KLP=N3 (2, LP=N3 = κ5-2,5-[(4- i PrC6H4)­N3P i Pr2]2N­(C4H2)−), that features two units of the rare phosphazide (RN3PR3) functionality was synthesized via an incomplete Staudinger reaction between K­[2,5-( i Pr2P)2N­(C4H2)] (1) and 4- i PrC6H4N3. The diphosphazide ligand was transferred to a thorium­(IV) metal center using salt metathesis strategies, yielding LP=N3ThCl3 (3), which contains two intact and coordinated phosphazides. Reaction of complex 3 with 3 equiv of LiCH2SiMe3 resulted in formation of the trialkyl thorium species LP=N3Th­(CH2SiMe3)3 (4). In contrast, attempts to synthesize an organothorium complex supported by the previously reported bisphosphinimine ligand LP=N (LP=N = κ3-2,5-[(4- i PrC6H4)­NP i Pr2]2N­(C4H2)−) afforded the cyclometalated dialkyl complex L*P=NTh­(CH2SiMe3)2 (6, L*PN = κ4-2-[(4- i PrC6H3)­NP i Pr2]-5-[(4- i PrC6H4)­NP i Pr2]­N­(C4H2)2–) and 1 equiv of free tetramethylsilane.