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Reactivity studies of the GeII→B complex L(Cl)Ge⋅BH3 (1; L=2-Et2NCH2-4,6-tBu2-C6H2) were performed to determine the effect on the GeII→B donation. N-coordinated compounds L(OtBu)Ge⋅BH3 (2) and [LGe⋅BH3]2 (3) were prepared. The possible tuning of the GeII→B interaction was proved experimentally, yielding compounds 1-PPh2-8-(LGe)-C10H6 (4) and L(Cl)Ge⋅GaCl3 (5) without a GeII→B interaction. In 5, an unprecedented GeII→Ga coordination was revealed. The experimental results were complemented by a theoretical study focusing on the bonding in 1−5. The different strength of the GeII→E (E=B, Ga) donation was evaluated by using energy decomposition analysis. The basicity of different L(X)Ge groups through proton affinity is also assessed.

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., The first examples of monomeric Group 13 diphosphanide and diarsanide compounds, (Dipp2Nacnac)M(EH2)2 (Dipp2Nacnac=HC[C(Me)N(Ar)]2, Ar: Dipp=2,6‐iPr2C6H3, E=P, M=Al, Ga, In; E=As, M=Al, Ga), were successfully synthesized. In these compounds the metal center is bound to two terminal PH2 and AsH2 groups, respectively.