Synthesis and structure of new compounds with Zn-Ga bonds. Insertion of the gallium(I) bisimidinate Ga(DDP) into Zn-X (X = CH₃, CI) and the homoleptic complex cation [Zn(GaCp*)₄]²⁺

Insertion reactions of the low-valent group 13 bisimidinate ligand Ga(DDP) {DDP = 2-[(2,6-diisopropylphenyl)-amino]-4-[(2,6-diisopropylphenyl)imino]-2- pentene} into Zn-Me and Zn-Cl bonds are reported. The reaction of ZnMe ₂ with 2 equiv of Ga(DDP) yields the double-insertion product [{(DDP)GaMe}₂Zn] (1), whereas the insertion of Ga(DDP) into the Zn-Cl bond of ZnCl₂ in tetrahydrofuran (THF) leads to the monoinsertion product [{(DDP)-GaCl)ZnCl(THF)₂] (2). Treatment of 2 with Na[BAr ^F] results in the salt [{THF·Ga(DDP)}Zn(THF)(μ-Cl)] ₂[BAr^F]₂ (3), with two Cl atoms bridging the Zn centers. The structural features of the Zn-Ga-bonded compounds 1-3 were compared with related complexes and in particular with the compound [Zn(GaCp*)₄][BAr^F]₂ (4), which was synthesized by the reaction of ZnMe₂, [H(OEt₂) ₂][BAr^F], and GaCp* in fluorobenzene. The complex cation [Zn(GaCp*)₄]²⁺ of 4 relates to previously reported d¹⁰ analogues [M(GaCp*)₄] (M = Ni, Pd, R). All new compounds were fully characterized by elemental analysis, NMR spectroscopy, and single-crystal X-ray diffraction analysis.