Monomeric β‐Diketiminato Group 13 Metal Dipnictogenide Complexes with Two Terminal EH(2) Groups (E=P, As)

The pnictogenyl Group 13 compounds (Dipp(2)Nacnac)M[E(SiMe(3))(2)]Cl and (Dipp(2)Nacnac)M(EH(2))(2) (Dipp(2)Nacnac=HC[C(Me)N(Ar)](2), Ar: Dipp=2,6‐iPr(2)C(6)H(3); M=Al, Ga, In; E=P, As) were successfully synthesized. The salt metathesis between (Dipp(2)Nacnac)MCl(2) and LiE(SiMe(3))(2) only led to monosubstituted compounds (Dipp(2)Nacnac)M[E(SiMe(3))(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 SiMe(3) groups in 1–4, the reactions of the corresponding halides with LiPH(2)⋅DME (or KAsH(2)) facilely yielded the dipnictogenide compounds (Dipp(2)Nacnac)M(EH(2))(2) (E=P, M=Al (5), Ga (6), In (7); E=As, M=Al (8), Ga (9)), avoiding the use of flammable and toxic PH(3) and AsH(3) 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 PH(2) and AsH(2) groups, respectively. In contrast to the successful synthesis of the indium diphosphanide (Dipp(2)Nacnac)In(PH(2))(2), the reaction of (Dipp(2)Nacnac)InCl(2) with KAsH(2) led to an indium mirror due to the instability of the target product.