Die elektronische Struktur einfacher Stickstoff-und sauerstoffhaltiger Verbindungen

✍ Scribed by J. Kuhn; W. Hug; R. Geiger; G. Wagnière

• Publisher: John Wiley and Sons
• Year: 1971
• Tongue: German
• Weight: 815 KB
• Volume: 54
• Category: Article
• ISSN: 0018-019X
• DOI: 10.1002/hlca.19710540764

✦ Synopsis

A general review is given of the UV.-spectroscopic properties of some simple molecules containing the N-N and N-0 bond, respectively. The electronic structure of nitrosomethane, azomethane, trimethylamine oxide, azomethane N, "-dioxide, nitromethane, methyl nitrite are reinvestigated by the SCF-CI method, within the frame of thc all-valence CNDO procedure. These calculations confirm a number of older assignments, but also allow predictions concerning some not settled questions. For instance, nitroalkanes should exhibit not one but two %-n* transitions, namely a t 275 nm and around 350 nm. This prediction agrees with conclusions by Djerassi and 4-0-workers on the spectra of some nitrosteroids.

Particular attention is given to the symmetry and relative energetic position of nonbonding orbitals. The question of "basicity" and "ease of protonation" is discussed in relation to it. Calculations on the overall charge distribution complement this investigation.