The present report describes the preparation and characterization of several N-2-(trimethylsilyl)ethyl-N-nitrosocarbamates, designed as precursors to thermally unstable secondary N-nitrosocarbamate anions via fluoride-assisted cleavage. X-ray structural studies demonstrate that the core N-nitrosocarbamate moiety has a nearly planar geometry, with an s-E orientation at the N–N bond. DFT calculations (B3LYP/6-31+G(d)) reproduce accurately the structural features of the title compounds and detailed conformational analysis at the same level of theory addresses the long-standing issue of preferred geometries for three classes of related structures: N-nitrosocarbamates, N-nitrosoureas and N-nitrosoamides. Desilylation studies demonstrate that both the solvent and the fluoride concentration influence the rate of the process.
- Analytical Chemistry,
- Biochemical Phenomena, Metabolism, and Nutrition,
- Chemical and Pharmacologic Phenomena,
- Chemistry,
- Environmental Chemistry,
- Inorganic Chemistry,
- Materials Chemistry,
- Medical Biochemistry,
- Medicinal-Pharmaceutical Chemistry,
- Organic Chemistry,
- Other Chemistry and
- Physical Chemistry
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