The pnictogenyl Group 13 compounds (Dipp₂Nacnac)M[E(SiMe₃)₂]Cl and (Dipp₂Nacnac)M(EH₂)₂ (Dipp₂Nacnac=HC[C(Me)N(Ar)]₂, Ar: Dipp=2,6-iPr₂C₆H₃; M=Al, Ga, In; E=P, As) were successfully synthesized. The salt metathesis between (Dipp₂Nacnac)MCl₂ and LiE(SiMe₃)₂ only led to monosubstituted compounds (Dipp₂Nacnac)M[E(SiMe₃)₂]Cl [E=P, M=Ga(1), In (2); E=As, M=Ga (3), In (4)], regardless of the stoichiometric ratios used. In contrast to the steric effect of the SiMe₃ groups in 1–4, the reactions of the corresponding halides with LiPH₂⋅DME (or KAsH₂) facilely yielded the dipnictogenide compounds (Dipp₂Nacnac)M(EH₂)₂ (E=P, M=Al (5), Ga (6), In (7); E=As, M=Al (8), Ga (9)), avoiding the use of flammable and toxic PH₃ and AsH₃ for their synthesis. The compounds 5–9 are the first examples of monomeric Group 13 diphosphanides and diarsanides in which the metal center is bound to two terminal PH₂ and AsH₂ groups, respectively. In contrast to the successful synthesis of the indium diphosphanide (Dipp₂Nacnac)In(PH₂)₂, the reaction of (Dipp₂Nacnac)InCl₂ with KAsH₂ led to an indium mirror due to the instability of the target product.