Heteroorganic betaines

Abstract

The structures of 6,6-dimethyl-6-silafulvene C₅H₄SiMe₂ (3), its donor-acceptor complex with ammonia. C₅H₄SiMe₂·NH₃, dimethylfulvene, a number of cyclopentadienylides, methylenetrimethylphosphorane (6), and silicon-containing organophosphorus betaine⁻C₅H₄SiMe₂CH₂PMe₃ ⁺ (13), the product of nucleophilic addition of6 to3, were calculated using the density functional approach. For compound13, the potential energy minimum corresponds to the conformation withgauche-arrangement of the cyclopentadienyl anionie and trimethylphosphonium cationic centers and a C−Si−C−P dihedral angle of 30.5°, which is due to the Coulomb attraction between these centers. According to calculations, betaine13 is rather stable toward decomposition into3 and6 (ΔH ^o=42 kcal mol⁻¹, ΔG ^Δ=30 kcal mol⁻¹). The main channel of thermal decomposition of compound13 involves an intramolecular nucleophilic substitution, which proceeds with elimination of trimethylphosphine and results in 1,1-dimethyl-1-silaspiro[2,4]hepta-4,6-diene, which then undergoes a ready and irreversible isomerization into 6,6-dimethyl-6-silabicyclo[3.2.0]hepta-1,3-diene owing to the [1.5]-sigmatropic shift of the C−Si bond.