Multinuclear NMR study of the solution structure and reactivity of tris(trimethylsilyl)methyllithium and its iodine ate complex.
作者： Hans J. Reich , William H. Sikorski , Aaron W. Sanders , Amanda C. Jones , Kristin N. Plessel
DOI: 10.1021/JO802032D
关键词:
摘要: The extreme steric bulk of tris(trimethylsilyl)methyl derivatives (1-X) provides interesting structural and dynamic behavior for study. Dynamic NMR studies on 1-SePh 1-I showed restricted rotation around the C−Si bonds each trimethylsilyl groups. An extensive multinuclear study natural abundance 6Li 13C enriched 1-Li revealed three species in THF-containing solvents, a dimer 1T, two monomers, contact ion pair 1C, solvent separated 1S. Observed barriers interconversion aggregates were unusually high (ΔG⧧ ca. 9 kcal/mol exchange 1S ΔG⧧41 = 16.4 1T with 1C 1S), allowing reactivity aggregate individually. We can show that is at least 50 times as reactive 5 × 1010 toward MeI. large difference allowed further mechanism lithium−iodine characterization intermediate iodine ate ...
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