Fig. 4: Synthesis and structures of 5a, and 6b,c. A.
From: Carbene-activated stannylenes to access selective C(sp3)–H bond scission at the steric limit
Reactivity of MesTerSn{N(SiMe3)2} (1a), DippTerSn{N(SiMe3)2} (1b) and TippTerSn{N(SiMe3)2} (1c) towards IiPr2Me2 to yield the C–H activation product 5a, and doubly C–H activation products 6b,c. Conditions (i) benzene, r.t. –60 °C; (ii) benzene, r.t.–90 °C. B: DFT-Calculated mechanism for the tuck-in formation of 5a from 1a and IiPr2Me2 at the BP86-D3BJ/Def2-TZVP (PCM = Benzene) level of theory. Gibbs free energies (ΔG298, kcal•mol−1) are given relative to the starting materials. C,D Molecular structures of 5a and 6b determined by single crystal X-ray crystallography. Anisotropic displacement parameters are drawn at the 50% probability level. Hydrogen atoms have been omitted where necessary for clarity, and in the case of 6b terphenyl substituents have also been omitted for clarity.
