Synthesis and Characterization of Silyldichloramines, Their Reactions with F Ions, Stability of N2Cl(2) and NCl(2), and Formation of NCl(3) (PREPRINT)
Abstract
Only two silyldichloramines, (C6H5)3SiNCl(2) and (CH3)3SiNCl(2), have been reported in the literature. The synthesis of the former was successfully repeated, and its structure was established by single crystal X-ray diffraction and vibrational spectroscopy. Attempts to prepare (CH3)3SiNCl(2) were unsuccessful, however, a new trialkylsilyldichloramine, t-BuMe2Si-NCl(2), was prepared and characterized by Raman and multinuclear NMR spectroscopy. The reaction of t-BuMe2SiNCl(2) with (CH3)4NF in CHF3 solution at -78 deg. C, followed by removal of all volatile products at -30 deg. C, produced the expected t-BuMe2SiF by-product and a white solid consisting of NCl(3) absorbed on Me4NCl. The NCl(3) could be reversibly desorbed from the substrate and was identified as a neat liquid at room temperature by Raman spectroscopy. The observed final reaction products are consistent with the formation of an unstable N(CH3)4+NCl(2)- intermediate which decomposes to N(CH3)4+Cl- and NCl molecules which can dimerize to N2Cl(2). Theoretical calculations confirm that NCl(2)- can readily lose Cl- and that N2Cl(2) also possesses a low barrier towards loss of N2 to give chlorine atoms and, thus, can account for the formation of NCl(3).
Document Details
- Document Type
- Technical Report
- Publication Date
- Jan 01, 2007
- Accession Number
- ADA462404
Entities
People
- Jerry A. Boatz
- Karl O. Christe
- Michael Gerken
- Ralf Haiges
- Stefan Schneider
- Thorsten Schroer