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 GaIcomplex 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 1reacts with GaMe3with insertion into two Ga–C bonds and formation of CyL2(GaMe)2GaMe (3), whereas the reaction with BiEt3only proceeds with activation of one Bi–C bond and formation of CyL2Ga(Et)Ga(BiEt2) (4). Reactions of 1with Sb2Et4and Bi2Ph4occurred with the insertion of both Ga centers into the E–E bonds and formation of CyL2(GaER2)2(ER2= SbEt26, BiPh27) with E–Ga–Ga–E motifs. Compounds 3–7were 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 GaIcenters, which were additionally studied by quantum chemical calculations.