Monomeric β-Diketiminato Group 13 Metal Dipnictogenide Complexes with Two Terminal EH2 Groups (E=P, As).

The pnictogenyl Group 13 compounds (Dipp2 Nacnac)M[E(SiMe3 )2 ]Cl and (Dipp2 Nacnac)M(EH2 )2 (Dipp2 Nacnac=HC[C(Me)N(Ar)]2 , Ar: Dipp=2,6-iPr2 C6 H3 ; M=Al, Ga, In; E=P, As) were successfully synthesized. The salt metathesis between (Dipp2 Nacnac)MCl2 and LiE(SiMe3 )2 only led to monosubstituted compounds (Dipp2 Nacnac)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 (Dipp2 Nacnac)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 (Dipp2 Nacnac)In(PH2 )2 , the reaction of (Dipp2 Nacnac)InCl2 with KAsH2 led to an indium mirror due to the instability of the target product.