Bond Activation by a Bimetallic GaIComplex: Avenue to Intermetallic Compounds

The synchronous participation of proximate metal centers in bimetallic complexes in a chemical transformation allows for the realization of otherwise unfeasible reaction pathways. Here, we investigated the potential of the bimetallic GaI complex CyL2Ga2 (1, CyL2 = 1,2-trans-C6H10[NC(Me)C(H)C(Me)N(Dip)]2, Dip = 2,6-i-Pr2C6H3) for the construction of intermetallic compounds by bond activation reactions of organometallic group 13 and 15 compounds. Compound 1 reacts with GaMe3 with insertion into two Ga–C bonds and formation of CyL2(GaMe)2GaMe (3), whereas the reaction with BiEt3 only proceeds with activation of one Bi–C bond and formation of CyL2Ga(Et)Ga(BiEt2) (4). Reactions of 1 with Sb2Et4 and Bi2Ph4 occurred with the insertion of both Ga centers into the E–E bonds and formation of CyL2(GaER2)2 (ER2 = SbEt2 6, BiPh2 7) with E–Ga–Ga–E motifs. Compounds 3–7 were characterized by heteronuclear NMR (1H, 13C{1H} (except 4)) and infrared (IR) spectroscopy as well as elemental analysis, and their solid-state structures were determined by single-crystal X-ray diffraction (sc-XRD). The structural features of the complexes hint at differing reaction pathways involving the two proximate GaI centers, which were additionally studied by quantum chemical calculations.