Synthesis, structure, and reactivity of a superbulky low‐valentbeta‑diketiminate Ga(I) complex

A low‐valent GaI complex with the superbulky b‐diketiminate ligand DIPePBDI (HC[C(Me)N‐DIPeP]2, DIPeP = 2,6‐C(H)Et2‐phenyl)) was obtained by reduction of (DIPePBDI)GaI2 (1) with KC8 in toluene. Considering that (BDI)GaI and analogue (BDI)AlI complexes are prone to decomposition and can generally only be obtained in low yields (20‐40%), the quantitative formation of (DIPePBDI)GaI (2) is remarkable and no doubt related to its excellent thermal stability even in refluxing toluene. Although the low‐valent metal center in 2 is sterically protected by the superbulky DIPePBDI ligand, it is readily oxidized by N2O to give intermediate (DIPePBDI)Ga=O which readily decomposed by abstracting a proton from the backbone Me‐substituent. Reaction with trimethylsilyl azide gave an intermediate imido complex (DIPePBDI)Ga=N(SiMe3)2 which reacted with a second equivalent of Me3SiN3 to a mixture of an azide/amido complex (DIPePBDI)GaN3[N(SiMe3)2] (4) and a tetrazagallole complex (DIPePBDI)Ga[N4(SiMe3)2] (5) in a 1:2 ratio. Whereas the azide/amido complex 4 could be structurally characterised, the tetraazagallole complex 5 was identified by NMR spectroscopy. DFT calculations on (DIPePBDI)GaI (2) and its reaction products complement this study.