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

Abstract

Abstract 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‐ i Pr 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.