Synthesis, Structural Studies and Desilylation Reactions of Some N-2-(Trimethylsilyl)ethyl-N-nitrosocarbamates

Author(s)

Arpitha Thakkalapally, University of Dayton
Vladimir Benin, University of DaytonFollow

Document Type

Article

Publication Date

5-2005

Publication Source

Tetrahedron

Abstract

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.

Inclusive pages

4939–4948

ISBN/ISSN

0040-4020

Document Version

Postprint

Comments

The document available for download is the authors' accepted manuscript, posted here in compliance with the publisher's policy on self-archiving.

Some differences may exist between this version and the publisher's version; as such, researchers wishing to quote directly from it are advised to consult the version of record, available at many libraries or from the publisher.

Permission documentation is on file.

Copyright

Copyright © 2005, Elsevier

Publisher

Elsevier

Volume

61

Peer Reviewed

yes

Issue

21

eCommons Citation

Thakkalapally, Arpitha and Benin, Vladimir, "Synthesis, Structural Studies and Desilylation Reactions of Some N-2-(Trimethylsilyl)ethyl-N-nitrosocarbamates" (2005). Chemistry Faculty Publications. 4.
https://ecommons.udayton.edu/chm_fac_pub/4